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United States Patent |
5,230,893
|
Gotou
,   et al.
|
July 27, 1993
|
Stable agrochemical compositions including alpha-unsaturated amine
derivative and acid incorporated into a carrier
Abstract
Stable agrochemical compositions are provided by incorporating at least one
of the .alpha.-unsaturated amine derivatives having the following formula:
##STR1##
wherein one of X.sup.1 and X.sup.2 is an electron attracting group and the
other is hydrogen or an electron attracting group; R.sup.1 is a group
attached through a nitrogen atom; R.sup.2 is hydrogen or a group attached
through a carbon, nitrogen, or oxygen atom; n is an integer of 0, 1, or 2;
and A is a substituted or unsubstituted heterocyclic group or a
substituted or unsubstituted cyclic hydrocarbon group; and salts thereof,
into an agrochemically acceptable solid carrier (clay minerals capable of
adsorption (including fuller's earth, terra alba, bentonite, and activated
fuller's earth), zeolite, activated charcoal, and .beta.-cyclodextrin,
etc.) under a pH 5.5 or less condition. The agrochemical (pesticidal)
compositions exert potent shelf life and light-resistance.
Inventors:
|
Gotou; Yukio (Tsukuba, JP);
Sawamura; Masatoshi (Tsukuba, JP);
Okauchi; Tetsuo (Osaka, JP)
|
Assignee:
|
Takeda Chemical Industries, Ltd. (Osaka, JP)
|
Appl. No.:
|
811651 |
Filed:
|
December 23, 1991 |
Foreign Application Priority Data
Current U.S. Class: |
424/409; 424/408 |
Intern'l Class: |
A01N 025/14; A01N 043/40 |
Field of Search: |
424/405,408,409,489
514/357,277
|
References Cited
U.S. Patent Documents
4133878 | Jan., 1979 | Gough | 424/255.
|
Foreign Patent Documents |
1094952 | Feb., 1981 | CA.
| |
281911 | Sep., 1988 | EP.
| |
0302389 | Feb., 1989 | EP.
| |
0302833 | Aug., 1989 | EP.
| |
0375907 | Jul., 1990 | EP.
| |
0383091 | Aug., 1990 | EP.
| |
2228003 | Aug., 1990 | GB.
| |
Other References
Jnl. Agric. Food Chem. 1991, 39, pp. 1320-1325, Rozen et al.,
"Photostabilization of
Tetrahydro-1-nitromethylene)-2H-1,3-thiaziadsorbedon Clays".
Chemical Abstracts, vol. III, No. 19, Nov. 6, 1989, Abstract No. 169376Y.
European Search Report.
|
Primary Examiner: Page; Thurman K.
Assistant Examiner: Levy; Neil
Attorney, Agent or Firm: Wegner, Cantor, Mueller & Player
Claims
What is claimed is:
1. An agrochemical composition which comprises:
(i) at least one .alpha.-unsaturated amine derivative having the following
formula:
##STR25##
wherein B.sup.a is a substituted or unsubstituted pyridyl or thiazolyl
group, and R.sup.8a, R.sup.9a and R.sup.10a are each independently
hydrogen; an alkyl, alkenyl, alkynyl, cycloalkyl, acyl, or alkoxycarbonyl
group, or an agrochemically acceptable salt thereof;
(ii) an acid whose dissociation constant is at least about
1.times.10.sup.-3 ; and
(iii) an agrochemically acceptable solid carrier which is capable of
adsorbing at least 5.0.times.10.sup.-2 mmol/g of the .alpha.-unsaturated
amine derivative or salt thereof from a solution or suspension adjusted to
a pH less than or equal to 5, both the .alpha.-unsaturated amine
derivative and the acid each being incorporated into the agrochemically
acceptable carrier.
2. The agrochemical composition according to claim 1, in which B.sup.a is a
group having the formula:
##STR26##
wherein Hal is halogen.
3. The agrochemical composition according to claim 1, comprising a compound
of the formula:
##STR27##
wherein R.sup.8 b, R.sup.9 b, and R.sup.10 b are each independently
hydrogen or an alkyl group, and Hal is halogen, or
##STR28##
wherein R.sup.8 c, R.sup.9 c, and R.sup.10 c are each independently
hydrogen or an alkyl group, and Hal is halogen, or an agrochemically
acceptable salt thereof.
4. The agrochemical composition according to claim 1, in which the
.alpha.-unsaturated amine derivative is
1-[N-(6-chloro-3-pyridylmethyl)-N-ethyl]amino-1-methylamino-2-nitroethylen
e or an agrochemically acceptable salt thereof.
5. The agrochemical composition according to claim 1, in which the acid is
selected from the group consisting of perchloric acid, hydrochloric acid,
sulfuric acid, nitric acid, phosphoric acid, aspartic acid, citric acid,
glutamic acid, oxalic acid, dichloroacetic acid, trichloroacetic acid,
fumaric acid, maleic acid, malonic acid, benzenesulfonic acid, and
isopropyl acid phosphate.
6. The agrochemical composition according to claim 1, in which the
agrochemically acceptable solid carrier is selected from the group
consisting of clay minerals capable of adsorption, zeolite, activated
charcoal, and .beta.-cyclodextrin.
7. The agrochemical composition according to claim 1, in which the solid
carrier is selected from the group consisting of montmorillonite-saponite
groups having 2:1 crystal structure type form and sepiolite having
double-chain crystal structure type form.
8. The agrochemical composition according to claim 1, in which the
agrochemically acceptable solid carrier is selected from the group
consisting of montmorillonite, beidellite, nontronite, saponite,
hectorite, sauconite, fuller's earth, terra alba, bentonite, and activated
fuller's earth.
9. The agrochemical composition according to claim 1, in which the
agrochemically acceptable solid carrier is fuller's earth.
10. The agrochemical composition according to claim 1, in which contains
one or more species of agrochemically active substances in addition to at
least one of the .alpha.-unsaturated amine derivatives.
Description
FIELD OF THE INVENTION
The present invention relates to stable agrochemical compositions
comprising an .alpha.-unsaturated amine derivative or a salt thereof. The
compositions of the present invention are useful as pesticidal agents for
controlling pests and worms in the agricultural field. The present
invention also relates to unique processes for preparing or formulating
said agrochemical compositions comprising the .alpha.-unsaturated amine
derivative or its salt. The processes are useful for stabilizing the
.alpha.-unsaturated amine derivative or its salt in agrochemical
formulations.
BACKGROUND OF THE INVENTION
.alpha.-Unsaturated amine derivatives or salts thereof having potent
inhibitory actions against harmful pests and the like have been employed
as insecticides. It has been found that such amines can be admixed with
other insecticides and/or fungicides to form advantageously valuable
agrochemical compositions (EPC Patent Application Laid Open No. 302,389;
corresponding to Japanese Patent Application Laid Open No. 171/1990).
Further, these compounds are of low toxicity to human beings, domestic
animals, fish and natural enemies of pests. For practical use, these
compounds are admixed with, for example, a carrier and/or bulking agent to
form a conventional solid formulation or preparation such as a dust,
granule, wettable powder, wettable granule, seed treating agent,
microgranule F, etc.
However, the .alpha.-unsaturated amine derivatives and their salts are
considerably unstable in the solid formulation wherein said amines are
admixed with a carrier and/or bulking agent (e.g. mineral powder). As
these compounds are stored at an ambient temperature (30.degree. C.) for
long time, they are gradually decomposed. As a result, this causes the
formulation to suffer a decrease in the content of the active ingredient.
Moreover, in the case where the amine is admixed with one or more species
of other agrochemical active substances in order to achieve high activity
in a wide range and simultaneous control for saving labor, the
decomposition and deterioration of such amines and their salts in the
mixed formulation is frequently more serious than that in the single
formulation.
The .alpha.-unsaturated amine derivatives and their salts have an
advantageous property for the environment because of their relatively
rapid photodegradation. However, there is a possibility that the
preparation could decrease high pesticidal activity by the decomposition
of said amines due to sunlight in the case of sprinkling on paddy fields,
or uplands.
In general, various techniques for stabilizing agrochemicals have been
developed (EPC Patent Application Laid Open No. 280,289; corresponding to
Japanese Patent Application Laid Open No. 4/1989 and Japanese Patent
Application Laid Open No. 4209/1987). Nevertheless, such prior art
techniques cannot solve the problems as described above.
It is still desired to develop a stable agrochemical formulation comprising
the .alpha.-unsaturated amine derivative or its salt.
SUMMARY OF THE INVENTION
Thus, it is the object of the present invention to provide improved
agrochemical compositions which have potent stability and excellent
prolonged preventive activity against pests. Further objects of the
present invention are to provide agrochemical compositions comprising an
.alpha.-unsaturated amine derivative or a salt thereof together with at
least one of other agrochemically active substances.
The present invention provides novel agrochemical compositions which
comprise
(i) at least one .alpha.-unsaturated amine derivative having the following
formula:
##STR2##
wherein one of X.sup.1 and X.sup.2 is an electron attracting group and the
other is hydrogen or an electron attracting group; R.sup.1 is a group
attached through a nitrogen atom; R.sup.2 is hydrogen or a group attached
through a carbon, nitrogen, or oxygen atom; n is an integer of 0, 1, or 2;
and A is a substituted or unsubstituted heterocyclic group or a
substituted or unsubstituted cyclic hydrocarbon group; and an
agrochemically acceptable salt thereof, and
(ii) an acid with an agrochemically acceptable solid carrier, and
preparations thereof.
The present invention is based on the observation that agrochemically
active substances are stabilized advantageously in agrochemical
compositions containing at least an acid and an agrochemically acceptable
solid carrier.
The present invention preferably provides novel agrochemical compositions
which comprise
(i) at least one .alpha.-unsaturated amine derivative having the following
formula:
##STR3##
wherein B is a substituted or unsubstituted 5- or 6-membered heterocyclic
group; and R.sup.8, R.sup.9 and R.sup.10 are each independently hydrogen
or a substituted or unsubstituted hydrocarbon group; and an agrochemically
acceptable salt thereof, and
(ii) an acid with an agrochemically acceptable solid carrier, and
preparations thereof.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to an agrochemical composition comprising at
least one .alpha.-unsaturated amine derivative of the formula [I] or its
salt, which exerts improved stability. The composition according to the
present invention may contain one or more other agrochemically active
substances in addition to the compound [I].
The present invention also relates to a method for preparing or formulating
a stable agrochemical composition comprising at least one
.alpha.-unsaturated amine derivative of the formula [I] or its salt,
optionally in admixture with one or more other agrochemically active
substances.
The present invention relates importantly to an agrochemical composition
comprising at least one .alpha.-unsaturated amine derivative of the
formula [II] or its salt, which exerts improved stability. The composition
according to the present invention may contain one or more other
agrochemically active substances in addition to the compound [II].
In the foregoing formula [I], one of X.sup.1 and X.sup.2 represents an
electron attracting group and the other represents hydrogen or an electron
attracting group. Examples of the electron attracting group for X.sup.1
and X.sup.2 include cyano; nitro; alkoxycarbonyl (e.g. C.sub.1-4
alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl);
hydoxycarbonyl; C.sub.8-10 aryloxycarbonyl groups such as
phenyloxycarbonyl; heterocyclyloxycarbonyl groups such as
pyridyloxycarbonyl and thienyloxycarbonyl (wherein the heterocyclic group
includes those mentioned hereinafter); C.sub.1-4 alkylsulfonyl groups
optionally substituted with 1 to 3 halogens, etc. such as methylsulfonyl,
trifluoromethylsulfonyl, and ethylsulfonyl; aminosulfonyl; di-C.sub.1-4
alkoxyphosphoryl such as diethoxyphosphoryl; C.sub.1-4 acyl groups
including alkanoyl optionally substituted with halogen, etc. such as
acetyl, trichloroacetyl and trifluoroacetyl; carbamoyl; C.sub.1-4
alkylsulfonylthiocarbamoyl such as methylsulfonylthiocarbamoyl; and the
like.
One of X.sup.1 and X.sup.2 may include halogens such as fluorine, chlorine,
bromine and iodine. X.sup.1 and X.sup.2 may also be taken together with
the nitrogen to which they are attached to form a ring such as
##STR4##
Preferred examples of the group represented by the formula:
##STR5##
include O.sub.2 N--CH.dbd., etc.
In the foregoing formula [I], R.sup.1 represents a group attached through a
nitrogen atom, including a group represented by the formula:
##STR6##
wherein R.sup.6 is hydrogen; alkyl (e.g. C.sub.1-6 alkyl such as methyl,
ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and n-hexyl, etc.);
C.sub.6-10 aryl such as phenyl, naphthyl and lower alkyl naphthyl; aralkyl
(e.g. C.sub.7-9 aralkyl such as benzyl, naphthylmethyl, etc.); a
heterocyclic group including those mentioned hereinafter (e.g. pyridyl,
etc.); C.sub.1-4 acyl including alkanoyl such as formyl, acetyl and
propionyl; C.sub.6-10 arylcarbonyl such as benzoyl; alkoxycarbonyl (e.g.
C.sub.1-4 alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl);
C.sub.8-10 aryloxycarbonyl such as phenyloxycarbonyl;
heterocyclyloxycarbonyl such as furyloxycarbonyl (wherein the heterocyclic
group includes those mentioned hereinafter); C.sub.6-10 arylsulfonyl such
as phenylsulfonyl; alkylsulfonyl (e.g. C.sub.1-4 alkylsulfonyl such as
methylsulfonyl); dialkoxyphosphoryl (e.g. di-C.sub.1-4 alkoxyphosphoryl
such as diethoxyphosphoryl); alkoxy (e.g. C.sub.1-4 alkoxy such as
methoxy, and ethoxy); hydroxyl; amino; dialkylamino (e.g. di-C.sub.1-4
alkylamino such as dimethylamino, and diethylamino); acylamino (e.g.
C.sub.1-4 acylamino such as formylamino, acetylamino, and propionylamino);
alkoxycarbonylamino (e.g. C.sub.1-4 alkoxycarbonylamino such as
methoxycarbonylamino); alkylsulfonylamino (e.g. C.sub.1-4
alkylsulfonylamino such as methylsulfonylamino); dialkoxyphosphorylamino
(e.g. di-C.sub.1-4 alkoxyphosphorylamino such as diethoxyphosphorylamino);
aralkyloxy (e.g. C.sub.7-9 aralkyloxy such as benzyloxy and other
phenylalkoxy); alkoxycarbonylalkyl (e.g. C.sub.1-4
alkoxycarbonyl-C.sub.1-4 alkyl such as methoxycarbonylmethyl); etc. and
R.sup.7 is hydrogen; alkyl (e.g. C.sub.1-4 alkyl such as methyl and
ethyl); cycloalkyl (e.g. C.sub.3-6 cycloalkyl such as cyclohexyl); alkenyl
(e.g. C.sub.2-4 alkenyl such as vinyl and allyl); cycloalkenyl (e.g.
C.sub.3-6 cycloalkenyl such as cyclohexenyl); alkynyl (e.g. C.sub.2-4
alkynyl such as ethynyl); etc. wherein the alkyl, the cycloalkyl, the
cycloalkenyl, and the alkynyl may further have 1 to 3 substituents
selected from hydroxy, C.sub.1-4 alkoxy such as methoxy and ethoxy,
di-alkylamino such as dimethylamino, C.sub.1-4 alkylthio such as
isopropylthio and n-propylthio, C.sub.1-3 acylamino such as acetylamino,
C.sub.1-4 alkylsulfonylamino such as methylsulfonylamino, tri-C.sub.1-4
alkylsilyl such as trimethylsilyl, pyridyl or thiazolyl which may be
substituted with 1 to 3 halogens, or R.sup.6 and R.sup.7, taken together
with the nitrogen to which they are attached, may form a 5 or 6-membered
cyclic amino group such as
##STR7##
Preferred examples of the group attached through a nitrogen atom for
R.sup.1 include an amino group optionally substituted with alkyl, aryl,
aralkyl, a heterocyclyl, acyl, alkoxycarbonyl, aryloxycarbonyl,
heterocyclyloxycarbonyl, arylsulfonyl, alkylsulfonyl, dialkoxyphosphoryl,
cycloalkyl, alkenyl, cycloalkenyl, alkynyl, or the like as described
herein for R.sup.6 and R.sup.7 (e.g. disubstituted amino such as
di-C.sub.1-6 alkylamino and N-C.sub.1-6 alkyl-N-formylamino;
monosubstituted amino such as mono-C.sub.1-6 alkylamino; and unsubstituted
amino); a hydrazino group optionally substituted with alkyl, acyl,
alkoxycarbonyl, alkylsulfonyl, dialkoxyphosphoryl, or the like as
described hereinafter for R.sup.3 ; a hydroxyamino group optionally
substituted with alkyl, aralkyl, or the like as described hereinafter for
R.sup.3.
Specifically, preferred examples of the group for R.sup.1 is the group
represented by the formula:
##STR8##
wherein
R.sup.6 and R.sup.7 have the same meanings as defined above.
R.sup.2 represents hydrogen or a group attached through a carbon, nitrogen,
or oxygen atom.
Examples of the group attached through a carbon atom for R.sup.2 include
C.sub.1-3 acyl (including alkanoyl) such as formyl, acetyl and propionyl;
alkyl (e.g. C.sub.1-4 alkyl such as methyl, ethyl, n-propyl, i-propyl,
n-butyl, i-butyl, sec-butyl, etc.); alkenyl (e.g. C.sub.2-4 alkenyl such
as vinyl and allyl); cycloalkyl (e.g. C.sub.3-6 cycloalkyl such as
cyclopentyl and cyclohexyl); C.sub.6-10 aryl such as phenyl, etc.; aralkyl
(e.g. C.sub.7-9 aralkyl such as benzyl, etc.); a heterocyclic group
attached through a carbon atom, including those mentioned hereinafter
(e.g. 3- or 4-pyridyl, etc.); and the like. These groups may have 1 to 3
substituent groups which are the same or different. Examples of such
substituent groups include C.sub.1-4 alkylthio such as methylthio, and
ethylthio; C.sub.1-4 alkoxy such as methoxy, and ethoxy; mono- or
di-C.sub.1-4 alkylamino such as methylamino, and dimethylamino; C.sub.1-4
alkoxycarbonyl such as methoxycarbonyl and ethoxycarbonyl; C.sub.1-4
alkylsulfonyl such as methylsulfonyl and ethylsulfonyl; halogen such as
fluorine, chlorine, bromine and iodine; C.sub.1-4 acyl (including
alkanoyl) such as acetyl; benzoyl; phenylsulfonyl; pyridyl; etc.
Examples of the group attached through a nitrogen atom for R.sup.2 include
those mentioned for R.sup.1.
Examples of the group attached through an oxygen atom for R.sup.2 include
alkoxy (e.g. C.sub.1-4 alkoxy such as methoxy, and ethoxy); cycloalkyloxy
(e.g. C.sub.3-6 cycloalkyloxy such as cyclohexyloxy); alkenyloxy (e.g.
C.sub.2-4 alkenyloxy such as vinyloxy and allyloxy); cycloalkenyloxy (e.g.
C.sub.3-6 cycloalkenyloxy such as cyclohexenyloxy); alkynyloxy (e.g.
C.sub.2-4 alkynyloxy such as ethynyloxy); C.sub.6-10 aryloxy such as
phenyloxy and naphthyloxy; heterocyclyloxy wherein the heterocyclic group
includes those mentioned hereinafter (e.g. thienyloxy, etc.); and
hydroxyl. These groups may have 1 to 3 substituent groups which are the
same or different. Examples of such substituent groups include halogen
such as fluorine, chlorine, and bromine; phenyl; etc.
Preferred examples of the group for R.sup.2 are groups attached through a
carbon, nitrogen, or oxygen atom, including formyl; alkyl (e.g. C.sub.1-4
alkyl such as methyl and ethyl) optionally substituted with C.sub.1-4
alkylthio, C.sub.1-4 alkoxy, mono- or di-C.sub.1-4 alkylamino, C.sub.1-4
alkoxycarbonyl, C.sub.1-4 alkylsulfonyl, halogen such as fluorine and
chlorine, acetyl, benzoyl, phenylsulfonyl, pyridyl, or the like as
mentioned above; optionally substituted amino (e.g. the optionally
substituted amino as mentioned for R.sup.1); hydroxyl optionally
substituted with C.sub.1-4 alkyl, C.sub.3-6 cycloalkyl, C.sub.2-4 alkenyl,
C.sub.3-6 cycloalkenyl, C.sub.2-4 alkynyl, C.sub.6-10 aryl, heterocyclyl
or the like (e.g. C.sub.1-4 alkoxy such as methoxy, and ethoxy); and the
like.
n is 0, 1 or 2.
The group --C.sub.n H.sub.2n -- in the formula [1] represents a single
bond, --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, or
##STR9##
preferably a single bond or --CH.sub.2 --.
A represents a heterocyclic group (e.g. a heterocyclic group optionally
substituted with 1 to three substituents as described hereinbelow,
especially the substituent (i), (iv), (viii), (xvii), (xLvi), or
(xLviii)).
Examples of A include 3-pyridyl, 6-chloro-3-pyridyl, 6-methoxy-3-pyridyl,
6-methyl-3-pyridyl, 6-bromo-3-pyridyl, 6-fluoro-3-pyridyl,
2-chloro-5-thiazolyl, 4-pyridyl, 2-pyrazinyl, 2-thiazolyl, 4-thiazolyl,
3-quinolyl, and the like.
A also represents a cyclic hydrocarbon group (e.g. a cyclic hydrocarbon
group optionally substituted with 1 or two substituents as described
hereinafter, especially the substituent (xvii)).
Examples of such groups include C.sub.3-6 cycloalkyl such as cyclopropyl,
cyclohexyl, and phenyl, p-chlorophenyl, and the like.
Preferred examples of the heterocyclic group for A are optionally
substituted pyridyl or thiazolyl such as 3-pyridyl, 4-pyridyl,
6-chloro-3-pyridyl, 6-bromo-3-pyridyl, 6-fluoro-3-pyridyl, and
2-chloro-5-thiazolyl.
Preferred examples of the cyclic hydrocarbon group for A are halogenophenyl
such as p-chlorophenyl.
The alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl,
heterocyclyl, and cyclic hydrocarbon groups for X.sup.1, X.sup.2, R.sup.1,
R.sup.2, R.sup.6, R.sup.7 and A include those mentioned below, optionally
substituted with 1 to 5 substituents such as (i) to (Lii) listed below.
The alkyl group has preferably 1 to about 20 carbon atoms, more preferably
1 to 8 carbon atoms. The alkyl group may have a straight or branched
chain.
Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl,
butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl,
2-ethylhexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, octadecyl, nonadecyl, eicocyl, and the like.
The cycloalkyl group has preferably 3 to about 6 carbon atoms, and
includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
and the like.
The alkenyl group, which may be straight or branched, has preferably 2 to
about 6 carbon atoms, and includes, for example, vinyl, allyl,
isopropenyl, methacryl, 1,1-dimethylallyl, 2-butenyl, 2-pentenyl,
4-pentenyl, 5-hexenyl, and the like.
The cycloalkenyl group, which may be branched, has preferably 3 to about 6
carbon atoms, and includes, for example, 1-cyclopropenyl, 2-cyclopropenyl,
1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl,
3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl,
1,3-cyclohexadien-1-yl, 1,4-cyclohexadien-1-yl, 1,3-cyclopentadien-1-yl,
2,4-cyclopentadien-1-yl, and the like.
The alkynyl group, which may be straight or branched, has preferably has 2
to about 6 carbon atoms, and includes, for example, ethynyl, propargyl,
2-butyn-1-yl, 3-butyn-1-yl, 3-butyn-2-yl, 1-pentyn-3-yl, 3-pentyn-1-yl,
4-pentyn-2-yl, 3-hexyn-1-yl, and the like.
The aryl group includes, for example, phenyl, naphthyl and the like.
The aralkyl group includes, for example, benzyl, phenethyl, naphthylmethyl
and the like.
The heterocyclic group is a cyclic group containing only the same
heteroatoms or a cyclic group containing two or more different
heteroatoms, e.g. a heterocyclic group having a single or fused ring with
5 to 8 ring members in each ring and having from one to five heteroatoms
in each ring independently selected from oxygen, nitrogen and sulfur.
Examples of the heterocyclic group include 2- or 3-thienyl, 2- or 3-furyl,
2- or 3-pyrrolyl, 2-, 3- or 4-pyridyl, 2-, 4- or 5-oxazolyl, 2-, 4- or
5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-imidazolyl, 3-, 4- or
5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 3- or 5-(1,2,4-oxadiazolyl),
1,3,4-oxadiazolyl, 3- or 5-(1,2,4-thiadiazolyl), 1,3,4-thiadiazolyl, 4- or
5-(1,2,3-thiadiazolyl), 1,2,5-thiadiazolyl, 1,2,3-triazolyl,
1,2,4-triazolyl, 1H- or 2H-tetrazolyl, N-oxide of 2-, 3- or 4-pyridyl, 2-,
4- or 5-pyrimidinyl, N-oxide of 2-, 4- or 5-pyrimidinyl, 3- or
4-pyridazinyl, pyrazinyl, N-oxide of 3- or 4-pyridazinyl, benzofuryl,
benzothiazolyl, benzoxazolyl, triazinyl, oxotriazinyl,
tetrazolo[1,5-b]pyridazinyl, triazolo[4,5-b]pyridazinyl, oxoimidazolyl,
dioxotriazinyl, pyrrolidinyl, piperidyl, pyranyl, thiopyranyl,
1,4-oxazinyl, morpholinyl, 1,4-thiazinyl, 1,3-thiazinyl, piperazinyl,
benzimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl,
quinazolinyl, quinoxalinyl, indolizinyl, quinolizinyl, 1,8-naphthyridinyl,
purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl,
phenanthridinyl, phenazinyl, phenothiazinyl, and phenoxazinyl.
The cyclic hydrocarbon group includes, for example, C.sub.3-6 cycloalkyl
such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, C.sub.3-6
cycloalkenyl such as 1-cyclopropenyl, 2-cyclobutenyl, 1-cyclohexenyl,
2-cyclohexenyl, and cyclopentyloxy, cyclohexyloxy, etc.
1,3-cyclohexadien-1-yl, and C.sub.6-10 aryl such as phenyl, and naphthyl.
(i) C.sub.1-4 Alkyl groups include, for example, methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc.
(ii) C.sub.3-6 Cycloalkyl groups include, for example, cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, etc.
(iii) C.sub.6-10 Aryl groups include, for example, phenyl, naphthyl, etc.
(iv) C.sub.1-4 Alkoxy groups include, for example, methoxy, ethoxy,
propoxy, isopropoxy, butoxy, tert-butoxy, etc.
(v) C.sub.3-6 Cycloalkoxy groups include, for example, cyclopropyloxy,
(vi) C.sub.6-10 Aryloxy groups include, for example, phenoxy, naphthyloxy,
etc.
(vii) C.sub.7-12 Aralkyloxy groups include, for example, benzyloxy,
2-phenethyloxy, 1-phenethyloxy, etc.
(viii) C.sub.1-4 Alkylthio groups include, for example, methylthio,
ethylthio, propylthio, butylthio, etc.
(ix) C.sub.3-6 Cycloalkylthio groups include, for example, cyclopropylthio,
cyclopentylthio, cyclohexylthio, etc.
(x) C.sub.6-10 Arylthio groups include, for example, phenylthio,
naphthylthio, etc.
(xi) C.sub.7-12 Aralkylthio groups include, for example, benzylthio,
2-phenethylthio, 1-phenethylthio, etc.
(xii) Mono-C.sub.1-4 alkylamino groups include, for example, methylamino,
ethylamino, propylamino, isopropylamino, butylamino, isobutylamino,
tert-butylamino, etc.
(xiii) Di-C.sub.1-4 alkylamino groups include, for example, dimethylamino,
diethylamino, dipropylamino, dibutylamino, N-methyl-N-ethylamino,
N-methyl-N-propylamino, N-methyl-N-butylamino, etc.
(xiv) C.sub.3-6 Cycloalkylamino groups include, for example,
cyclopropylamino, cyclopentylamino, cyclohexylamino, etc.
(xv) C.sub.6-10 Arylamino groups include, for example, anilino, etc.
(xvi) C.sub.7-12 Aralkylamino groups include, for example, benzylamino,
2-phenethylamino, 1-phenethylamino, etc.
(xvii) Halogens include, for example, fluorine, chlorine, bromine, iodine,
etc.
(xviii) C.sub.1-4 Alkoxycarbonyl groups include, for example,
methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl,
butoxycarbonyl, tert-butoxycarbonyl, isobutoxycarbonyl, etc.
(xix) C.sub.6-10 Aryloxycarbonyl groups include, for example,
phenoxycarbonyl, etc.
(xx) C.sub.3-6 Cycloalkoxycarbonyl groups include, for example,
cyclopropyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl,
etc.
(xxi) C.sub.7-12 Aralkyloxycarbonyl groups include, for example,
benzyloxycarbonyl, 1-phenethyloxycarbonyl, 2-phenethyloxycarbonyl, etc.
(xxii) C.sub.1-5 Alkanoyl groups include, for example, formyl, acetyl,
propionyl, butyryl, pivaloyl, etc.
(xxiii) C.sub.1-15 Alkanoyloxy groups include, for example, formyloxy,
acetyloxy, butyryloxy, pivaloyloxy, pentanoyloxy, hexanoyloxy,
hepanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy,
dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy, and the
like.
(xxiv) Optionally substituted carbamoyl groups include, for example,
carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N-ethylcarbamoyl,
N,N-diethylcarbamoyl, N-phenylcarbamoyl, pyrrolidinocarbamoyl,
piperidinocarbamoyl, piperazinocarbamoyl, morpholinocarbamoyl,
N-benzylcarbamoyl, etc.
(xxv) Optionally substituted carbamoyloxy groups include, for example,
N-methylcarbamoyloxy, N,N-dimethylcarbamoyloxy, N-ethylcarbamoyloyx,
N-benzylcarbamoyloxy, N,N-dibenzylcarbamoyloxy, N-phenylcarbamoyloxy, etc.
(xxvi) C.sub.1-4 Alkanoylamino groups include, for example, formylamino,
acetamido, propionamido, butyrylamido, etc.
(xxvii) C.sub.6-10 Arylcarbonylamino groups include, for example,
benzamido, etc.
(xxviii) C.sub.1-4 Alkoxycarbonylamino groups include, for example,
methoxycarbonylamino, ethoxycarbonylamino, butoxycarbonylamino,
tert-butoxycarbonylamino, etc.
(xxix) C.sub.7-12 Aralkyloxycarbonylamino groups include, for example,
benzyloxycarbonylamino, 4-methoxybenzyloxycarbonylamino,
4-nitrobenzyloxycarbonylamino, 4-chlorobenzyloxycarbonylamino, etc.
(xxx) Substituted sulfonylamino groups include, for example,
methanesulfonylamino, ethanesulfonylamino, butanesulfonylamino,
benzenesulfonylamino, toluenesulfonylamino, naphthalenesulfonylamino,
trifluoromethanesulfonylamino, 2-chloroethanesulfonylamino,
2,2,2-trifluoroethanesulfonylamino, etc.
(xxxi) Heterocyclic groups are cyclic groups each containing 1 to 5
heteroatoms selected from nitrogen, oxygen and sulfur and include, for
example, pyrrolidinyl, 2- or 3-pyrrolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or
5-imidazolyl, 2- or 3-furyl, 2-or 3-thienyl, 2-, 4- or 5-oxazolyl, 3-, 4-
or 5-isoxazolyl, 3-, 4-or 5-isothiazolyl, 2-, 4- or 5-thiazolyl,
piperidinyl, 2-, 3- or 4-pyridyl, piperazinyl, pyrimidinyl, pyranyl,
tetrahydropyranyl, tetrahydrofuryl, indolyl, quinolyl, 1,3,4-oxadiazolyl,
thieno[2,3-d]pyridyl, 1,2,3-thiadiazolyl, 1,3,4-thiadiazolyl,
1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, tetrazolyl, 4,
5-dihydro-1,3-dioxolyl, tetrazolo[1,5-b]pyridazinyl, benzothiazolyl,
benzoxazolyl, benzimidazolyl, benzothienyl, etc.
(xxxii) Heterocyclylthio, heterocyclyloxy, heterocyclylamino, and
heterocyclylcarbonylamino groups are heterocyclic groups attached through
sulfur, nitrogen, oxygen and carbonyl respectively wherein the
heterocyclyl portion is the above-mentioned group (xxxi).
(xxxiii) Di-C.sub.1-4 alkylphosphinothioylamino groups include, for
example, dimethylphosphinothioylamino, diethylphosphinothioylamino, etc.
(xxxiv) Alkoxyimino groups include, for example, methoxyimino, ethoxyimino,
2-fluoroethoxyimino, carboxymethoxyimino, 1-carboxy-1-methylethoxyimino,
2,2,2-trichloroethyloxycarbonylmethoxyimino,
1-(2,2,2-trichloroethyloxycarbonyl)-1-methylethoxyimino,
(2-aminothiazol-4-yl)methoxyimino, (1H-imidazol-4-yl)methoxyimino, etc.
(xxxv) C.sub.1-4 Alkylsulfonyloxy groups include, for example,
methanesulfonyloxy, ethanesulfonyloxy, butanesulfonyloxy, etc.
(xxxvi) C.sub.6-10 Arylsulfonyloxy groups include, for example,
benzenesulfonyloxy, toluenesulfonyloxy, etc.
(xxxvii) Di-C.sub.6-10 arylphosphinothioylamino groups include, for
example, diphenylphosphinothioylamino, etc.
(xxxviii) Optionally substituted thiocarbamoylthio groups include, for
example, thiocarbamoylthio, N-methylthiocarbamoylthio,
N,N-dimethylthiocarbamoylthio, N-ethylthiocarbamoylthio,
N-benzylthiocarbamoylthio, N,N-dibenzylthiocarbamoylthio,
N-phenylthiocarbamoylthio, etc.
(xxxix) Silyloxy groups include tri-C.sub.1-4 alkylsilyloxy groups such as
trimethylsilyloxy and tert-butyldimethylsilyloxy, mixed C.sub.1-4
alkyl-phenylsilyloxy groups such as tert-butyldiphenylsilyloxy, and
dimethylphenylsilyloxy, etc.
(xL) Silyl groups include tri-C.sub.1-4 alkylsilyl groups such as
trimethylsilyl and tert-butyldimethylsilyl, mixed C.sub.1-4
alkyl-phenylsilyl groups such as tert-butyldiphenylsilyl, and
dimethylphenylsilyl, etc.
(xLi) C.sub.1-4 Alkylsulfinyl groups include, for example, methylsulfinyl,
ethylsulfinyl, propylsulfinyl, butylsulfinyl, etc.
(xLii) C.sub.6-10 Arylsulfinyl groups include, for example, phenylsulfinyl,
naphthylsulfinyl, etc.
(xLiii) C.sub.1-4 Alkylsulfonyl groups include, for example,
methanesulfonyl, ethanesulfonyl, butanesulfonyl, etc.
(xLiv) C.sub.6-10 Arylsulfonyl groups include, for example,
benzenesulfonyl, toluenesulfonyl, etc.
(xLv) C.sub.1-4 Alkoxycarbonyloxy groups include, for example,
methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, etc.
(xLvi) C.sub.1-4 Haloalkyl groups include C.sub.1-4 alkyl groups with 1 to
4 halogen atoms such as trifluoromethyl, 1,1,2,2-tetrafluoroethyl,
difluoromethyl, monofluoromethyl, trichloromethyl, dichloromethyl,
monochloromethyl, and the like.
(xLvii) C.sub.1-4 Haloalkyloxy, C.sub.1-4 haloalkylthio, C.sub.1-4
haloalkylsulfinyl, and C.sub.1-4 haloalkylsulfonyl groups are, for
example, C.sub.1-4 haloalkyl groups attached through an oxygen, sulfur and
nitrogen atom, a sulfinyl and sulfonyl group, respectively wherein the
C.sub.1-4 haloalkyl portion is the above-mentioned group (xLvi).
(xLviii) Cyano, nitro, hydroxyl, carboxyl, sulfo (--SO.sub.3 H), and
phosphono (--PO.sub.3 H.sub.2).
(xLix) C.sub.1-4 Alkyloxysulfonyl groups include, for example,
methoxysulfonyl, ethoxysulfonyl, butoxysulfonyl, etc.
(L) C.sub.6-10 Aryloxysulfonyl groups include, for example,
phenoxysulfonyl, tolyloxysulfonyl, etc.
(Li) C.sub.7-12 Aralkyloxysulfonyl groups include, for example,
benzyloxysulfonyl, 2-phenethyloxysulfonyl, 1-phenethyloxysulfonyl, etc.
(Lii) Di-C.sub.1-4 alkyloxyphosphoryl groups include, for example,
dimethoxyphosphoryl, diethoxyphosphoryl, dibutoxyphosphoryl, etc.
Among the compounds represented by the above formula (I), preferred
examples of the invention are compounds of the formula:
##STR10##
wherein R.sup.1a is mono-C.sub.1-6 alkylamino, N-C.sub.1-6
alkyl-N-formylamino, or amino, R.sup.2a is C.sub.1-4 alkyl or C.sub.1-4
alkoxy and A.sup.a is chloropyridyl;
##STR11##
wherein R.sup.1b is mono-C.sub.1-6 alkylamino, or N-C.sub.1-6
alkyl-N-formylamino, and A.sup.a is of the same meaning as defined above;
##STR12##
wherein R.sup.1c is di-C.sub.1-6 alkylamino, R.sup.2b is hydrogen, formyl,
or C.sub.1-4 alkyl and A.sup.b is pyridyl or chloropyridyl; or
##STR13##
wherein each group is of the same meaning as defined above; or
agrochemically acceptable salts thereof.
The mono-C.sub.1-6 alkylamino groups for R.sup.1a and R.sup.1b in the
formulas [I.sup.a ], [I.sup.b ], and [I.sup.c ] include, for example,
monomethylamino, monoethylamino, mono-n-propylamino, mono-i-propylamino,
mono-n-butylamino, mono-i-butylamino, mono-n-hexylamino, etc. Preferred
examples of such mono-C.sub.1-6 alkylamino groups are mono-C.sub.1-4
alkylamino such as monomethylamino, and monoethylamino.
The N-C.sub.1-6 alkyl-N-formylamino groups for R.sup.1a and R.sup.1b
include, for example, N-methyl-N-formylamino, N-ethyl-N-formylamino,
N-n-propyl-N-formylamino, N-i-propyl-N-formylamino,
N-n-butyl-N-formylamino, N-n-hexyl-N-formylamino, etc. Preferred examples
of such N-C.sub.1-6 alkyl-N-formylamino groups are N-C.sub.1-4
alkyl-N-formylamino such as N-methyl-N-formylamino, and
N-ethyl-N-formylamino.
The di-C.sub.1-6 alkylamino groups for R.sup.1c include, for example,
dimethylamino, N-ethyl-N-methylamino, diethylamino, di-n-propylamino,
di-i-propylamino, di-n-butylamino, di-i-butylamino, di-n-pentylamino,
di-i-pentylamino, di-n-hexylamino, etc. Preferred examples of such
di-C.sub.1-6 alkylamino groups are di-C.sub.1-4 alkylamino such as
dimethylamino, N-ethyl-N-methylamino, and diethylamino.
The C.sub.1-4 alkyl groups for R.sup.2a and R.sup.2c include, for example,
those mentioned above for R.sup.2. Preferred examples of such C.sub.1-4
alkyl groups are methyl, ethyl, etc.
The C.sub.1-4 alkoxy groups for R.sup.2a include, for example, those
mentioned above for R.sup.2. Preferred examples of such C.sub.1-4 alkoxy
groups are methoxy, ethoxy, etc.
The chloropyridyl groups for A.sup.a and A.sup.b include, for example,
2-chloro-3-pyridyl, 4-chloro-3-pyridyl, 5-chloro-3-pyridyl,
6-chloro-3-pyridyl, 3-chloro-4-pyridyl, etc. Preferred examples of such
chloropyridyl groups are 6-chloro-3-pyridyl, etc.
The pyridyl groups for A.sup.b include, for example, 3-pyridyl, 4-pyridyl,
etc. Preferred examples of such pyridyl groups are 3-pyridyl, etc.
Among the compounds represented by the above formula (I), preferred
examples of the invention are compounds of the formula:
##STR14##
wherein X.sup.2a is hydrogen, C.sub.1-4 alkoxycarbonyl or C.sub.1-4
alkylsulfonylthiocarbamoyl; R.sup.2c is hydrogen, C.sub.1-3 acyl,
C.sub.1-4 alkyl, mono- or di-C.sub.1-4 alkoxy-C.sub.1-4 alkyl, C.sub.7-8
aralkyl, mono- or di-C.sub.1-4 alkylamino or C.sub.1-4 alkoxy; A.sup.c is
3- or 4-pyridyl, pyrazinyl, or 4- or 5-thiazolyl, optionally substituted
with halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy; R.sup.6a and R.sup.7a
are each hydrogen, lower alkyl, halogenated lower alkyl, or C.sub.1-4
acyl; n is of the same meaning as defined above.
##STR15##
wherein X.sup.2a is hydrogen, C.sub.1-4 alkoxycarbonyl or C.sub.1-4
alkylsulfonylthiocarbamoyl; R.sup.1d is amino, mono- or di-C.sub.1-4
alkylamino, N-C.sub.1-4 alkyl-N-C.sub.1-3 acylamino, C.sub.7-9
aralkylamino, halogenothiazolyl-C.sub.1-2 alkylamino, or C.sub.1-4
alkoxy-C.sub.1-2 alkylamino; R.sup.2c is hydrogen, C.sub.1-3 acyl,
C.sub.1-4 alkyl, mono- or di-C.sub.1-4 alkoxy-C.sub.1-4 alkyl, C.sub.7-8
aralkyl, mono- or di-C.sub.1-4 alkylamino or C.sub.1-4 alkoxy; n is 0, 1
or 2; A.sup.d is 3- or 4-pyridyl, pyrazinyl, or 5-thiazolyl, optionally
substituted with halogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy;
##STR16##
wherein X.sup.2 b is hydrogen, or C.sub.1-2 alkylsulfonylthiocarbamoyl;
R.sup.1 e is amino, mono- or di-C.sub.1-2 alkylamino, or N-C.sub.1-2
alkyl-N-formylamino; R.sup.2 d is hydrogen, or C.sub.1-3 acyl; and A.sup.e
is a group having the formula:
##STR17##
wherein Hal is halogen;
##STR18##
wherein X.sup.2 c is hydrogen, or methylsulfonylthiocarbamoyl; R.sup.1 f
is amino, methylamino, dimethylamino, or N-methyl-N-formylamino; R.sup.2 d
is hydrogen, formyl, or C.sub.1-2 alkyl; and A.sup.e is a group having the
formula:
##STR19##
wherein Hal is halogen; or
##STR20##
wherein R.sup.1 e is amino, mono- or di-C.sub.1-2 alkylamino, or
N-C.sub.1-2 alkyl-N-formylamino; R.sup.2 e is C.sub.1-2 alkyl, or formyl;
and Hal is halogen; or agrochemically acceptable salts thereof.
With regard to the formulas [I.sup.e ] to [I.sup.i ], the groups
represented by X.sup.2 a, X.sup.2 b, and X.sup.2 c ; R.sup.1 d, R.sup.1 e,
and R.sup.1 f ; R.sup.2 c, R.sup.2 d, and R.sup.2 e ; and A.sup.c,
A.sup.d, and A.sup.e are those mentioned herein for X.sup.2, R.sup.1,
R.sup.2, A, respectively. The groups represented by R.sup.6 a and the
groups represented by R.sup.7 a are those mentioned herein for R.sup.6 and
R.sup.7, respectively.
The compounds represented by the formula [I] and their salts can be
prepared by processes as disclosed in EPC Patent Application Laid Open No.
302,389 (corresponding to Japanese Patent Application Laid Open No.
171/1990) or processes analogous to the known methods.
In the foregoing formula [II], R.sup.8, R.sup.9, and R.sup.10 represents
hydrogen; C.sub.1-3 acyl groups including alkanoyl groups such as formyl,
acetyl, and propionyl; alkyl groups, for example, C.sub.1-4 alkyl groups
such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and
sec-butyl; alkenyl groups, for example, C.sub.2-4 alkenyl such as vinyl,
and allyl; alkynyl groups, for example, C.sub.2-4 alkynyl such as ethynyl
1-propynyl, and 2-propynyl; cycloalkyl groups, for example, C.sub.3-6
cycloalkyl groups such as cyclopentyl and cyclohexyl; or heterocyclic
groups bonded through the carbon atom thereon (including those mentioned
herein for B), for example, pyridyl groups such as 3- or 4-pyridyl.
These groups for R.sup.8, R.sup.9, and R.sup.10 may have 1 to 3 (preferably
1) substituent groups which are the same or different. Examples of such
substituent groups include but are not limited to C.sub.1-4 alkylthio
groups such as methylthio, and ethylthio; C.sub.1-4 alkoxy groups such as
methoxy, and ethoxy; mono- or di-C.sub.1-4 alkylamino groups such as
methylamino, ethylamino, and dimethylamino; C.sub.2-5 alkoxycarbonyl
groups such as methoxycarbonyl, and ethoxycarbonyl; C.sub.1-4
alkylsulfonyl groups such as methylsulfonyl, and ethylsulfonyl; halogens
such as fluorine, chlorine, bromine and iodine; C.sub.1-4 acyl groups
including alkanoyl groups such as acetyl; benzoyl; phenylsulfonyl; and
pyridyl.
Preferred examples for R.sup.8, R.sup.9, and R.sup.10 are hydrogen;
C.sub.1-3 acyl groups including alkanoyl groups such as formyl, acetyl,
and propionyl; and alkyl groups, for example, C.sub.1-4 alkyl groups such
as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and sec-butyl.
More preferred examples for R.sup.8, R.sup.9, and R.sup.10 are hydrogen;
C.sub.1-3 alkanoyl groups such as formyl, acetyl, and propionyl; and
C.sub.1-4 alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl,
i-butyl, and sec-butyl.
In the foregoing formula [II], B represents a substituted or unsubstituted
heterocyclic group having a single or fused ring with 5 or 6 ring members
in each ring. Specific examples of suitable five- or six-membered
heterocyclic groups include pyridyl groups such as 2-, 3- or 4-pyridyl,
thiazolyl groups such as 2-, 4- or 5- thiazolyl and pyrazinyl groups.
These heterocyclic groups may have 1 to 5 (preferably 1) substituent groups
which are the same or different. Examples of such substituent groups
include but are not limited to C.sub.1-4 alkyl groups such as methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl;
C.sub.1-4 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, and
tert-butoxy; C.sub.1-4 alkylthio groups such as methylthio, ethylthio,
propylthio, and butylthio; halogens such as fluorine, chlorine, bromine
and iodine; C.sub.1-4 haloalkyl groups such as trifluoromethyl,
1,1,2,2-tetrafluoroethyl, difluoromethyl, monofluoromethyl,
trichloromethyl, dichloromethyl, and monochloromethyl; C.sub.1-4
haloalkoxy groups; C.sub.1-4 haloalkylthio groups; C.sub.1-4
haloalkylsulfinyl groups; or C.sub.1-4 haloalkylsulfonyl groups wherein
said C.sub.1-4 haloalkyl group is attached through an oxygen or sulfur
atom, or a sulfinyl or sulfonyl group; cyano; nitro; hydroxyl; carboxyl;
sulfo (--SO.sub.3 H); and phosphono (--PO.sub.3 H.sub.2).
Preferred examples of B are five- or six-membered heterocyclic groups such
as pyridyl and thiazolyl which may be substituted with one or two
halogens. Specific examples of B are 3-pyridyl, 4-pyridyl, halogenopyridyl
such as 6-chloro-3-pyridyl, 6-bromo-3-pyridyl, 6-fluoro-3-pyridyl, and
5-bromo-3-pyridyl, 6-methoxy-3-pyridyl, 6-methyl-3-pyridyl, 2-thiazolyl,
4-thiazolyl, halogenothiazolyl such as 2-chloro-5-thiazolyl and
2-bromo-5-thiazolyl, 2-pyrazinyl.
More preferred examples of B are 3-pyridyl, 4-pyridyl, 6-chloro-3-pyridyl,
6-bromo-3-pyridyl, 6-fluoro-3-pyridyl, 5-bromo-3-pyridyl,
6-methoxy-3-pyridyl, 6-methyl-3-pyridyl, 2-thiazolyl, 4-thiazolyl,
2-chloro-5-thiazolyl, 2-bromo-5-thiazolyl, 2-pyrazinyl.
Among the compounds represented by the above formula [II], a preferred
embodiment is a compound of the formula:
##STR21##
wherein B.sup.a is a substituted or unsubstituted pyridyl or thiazolyl
group, and R.sup.8 a, R.sup.9 a, and R.sup.10 a are each independently
hydrogen; an alkyl, alkenyl, alkynyl, cycloalkyl, acyl, or alkoxycarbonyl
group, or an agrochemically acceptable salt thereof.
In the foregoing formula [II.sup.a ], a preferred embodiment of B.sup.a is
a halogenated group such as a group having the formula:
##STR22##
wherein Hal is halogen.
Among the compounds represented by the above formula [II.sup.a ], a more
preferred embodiment is a compound of the formula:
##STR23##
wherein R.sup.8 b, R.sup.9 b, and R.sup.10 b are each independently
hydrogen or an alkyl group, and Hal is halogen, or
##STR24##
wherein R.sup.8 c, R.sup.9 c, and R.sup.10 c are each independently
hydrogen or an alkyl group, and Hal is halogen, or an agrochemically
acceptable salt thereof.
The compounds represented by the formula [II] and their salts can be
prepared by processes known in the prior arts. The compounds represented
by the formula [II] and their salts can also be prepared by processes as
disclosed in EPC Patent Application Laid Open No. 302,389 (corresponding
to Japanese Patent Application Laid Open No. 171/1990) or processes
analogous to the known methods.
In the case where the compound [I] or [II] is obtained in its free form, it
can be converted into a corresponding salt by conventional methods. When
the compound [I] or [II] is obtained in its salt form, it can be converted
into the corresponding free form by conventional methods.
In the case where the compound [I] or [II] has at least one of acidic
groups such as carboxyl, sulfo (--SO.sub.3 H), and phosphono (--PO.sub.3
H.sub.2), the compound [I] or [II] can form a salt with a base. Examples
of such bases include inorganic bases such as sodium, potassium, lithium,
calcium, magnesium, and ammonia, and organic bases such as pyridine,
collidine, triethylamine, and triethanolamine.
In the case where the compound [I] or [II] has at least one of basic groups
such as amino or substituted amino, the compound [I] or [II] can be formed
an acid addition salt. Examples of such acid addition salts include salts
with inorganic acids such as hydrochloric acid, hydrobromic acid,
hydroiodic acid, nitric acid, sulfuric acid, and phosphoric acid, as well
as with organic acids such as acetic acid, benzoic acid, maleic acid,
fumaric acid, succinic acid, tartaric acid, citric acid, oxalic acid,
glyoxalic acid, asparaginic acid, methanesulfonic acid, methanedisulfonic
acid, 1,2-ethanedisulfonic acid, and benzenesulfonic acid.
Representative examples of .alpha.-unsaturated amine derivatives of the
formulas [I] and [II] which can be used in the composition according to
the present invention are:
(compound No.1)
1-[N-(6-chloro-3-pyridylmethyl)-N-methyl]amino-1-methylamino-2-nitroethyle
ne;
(compound No.2)
1-(6-chloro-3-pyridylmethyl)amino-1-dimethylamino-2-nitroethylene;
(compound No.3)
1-[N-(6-chloro-3-pyridylmethyl)-N-ethyl]amino-1-methylamino-2-nitroethylen
e;
(compound No.4)
1-[N-(6-chloro-3-pyridylmethyl)-N-methyl]amino-1-dimethylamino-2-nitroethy
lene;
(compound No.5)
1-[N-(6-chloro-3-pyridylmethyl)-N-ethyl]amino-1-(N-formyl-N-methyl)amino-2
-nitroethylene;
(compound No.6)
1-[N-(2-chloro-5-thiazolylmethyl)-N-ethyl]amino-1-methylamino-2-nitroethyl
ene;
(compound No.7)
1-[N-(2-chloro-5-thiazolylmethyl)]amino-1-dimethylamino-2-nitroethylene;
(compound No.8)
1-[N-(6-bromo-3-pyridylmethyl)-N-methyl]amino-1-methylamino-2-nitroethylen
e;
(compound No.9)
1-[N-(6-chloro-3-pyridylmethyl)-N-formyl]amino-1-dimethylamino-2-nitroethy
lene;
(compound No.10)
1-[N-(6-fluoro-3-pyridylmethyl)-N-methyl]amino-1-methylamino-2-nitroethyle
ne;
(compound No.11)
1-[N-ethyl-N-(6-fluoro-3-pyridylmethyl)]amino-1-methylamino-2-nitroethylen
e;
(compound No.12)
1-[N-(6-bromo-3-pyridylmethyl)-N-ethyl]amino-1-methylamino-2-nitroethylene
;
(compound No.13)
1-[N-(2-chloro-5-thiazolylmethyl)-N-methyl]amino-1-(N-formyl-N-methyl)amin
o-2-nitroethylene;
(compound No.14)
1-[N-(2-chloro-5-thiazolylmethyl)-N-ethyl]amino-1-(N-formyl-N-methyl)amino
-2-nitroethylene;
(compound No.15)
1-[N-(6-bromo-3-pyridylmethyl)-N-methyl]amino-1-(N-formyl-N-methyl)amino-2
-nitroethylene;
(compound No.16)
1-[N-(6-bromo-3-pyridylmethyl)-N-ethyl]amino-1-(N-formyl-N-methyl)amino-2-
nitroethylene;
(compound No.17)
1-[N-(6-bromo-3-pyridylmethyl)-N-formyl]amino-1-dimethylamino-2-nitroethyl
ene;
(compound No.18)
1-[N-(6-chloro-3-pyridylmethyl)-N-(2,2,2-trifluoroethyl)]amino-1-methylami
no-2-nitroethylene;
(compound No.19)
1-[N-(2-chloro-5-thiazolylmethyl)-N-formyl]amino-1-dimethylamino-2-nitroet
hylene;
(compound No.20)
1-(6-chloro-3-pyridylmethyl)amino-1-methylamino-2-nitroethylene;
(compound No.21)
1-amino-1-[N-(6-chloro-3-pyridylmethyl)-N-methyl]amino-1-methylamino-2-nit
roethylene;
and the like.
The .alpha.-unsaturated amine derivatives or salts thereof can be employed
as insecticide according to the techniques as disclosed in EPC Patent
Application Laid Open No. 302,389 (corresponding to Japanese Patent
Application Laid Open No. 171/1990).
The present inventors have found that the .alpha.-unsaturated amine
derivatives or salts thereof can be significantly stabilized during long
term storage and against light in agrochemical formulations by employing
acids and specific solid carriers.
The present inventors have also found that the .alpha.-unsaturated amine
derivatives or salts thereof can be incorporated into solid carriers
capable of adsorption, among various agrochemical bulking agents, whereby
it is possible to improve significantly the long term and light stability
of said .alpha.-unsaturated amine derivatives or salts thereof in the
formulation.
According to one embodiment, the present inventors have succeeded in
preparing a pH 5.5 or less aqueous solution (or suspension) of an
agrochemically active ingredient (.alpha.-unsaturated amine derivative or
its salt) and adding said solution (or suspension) to the above-mentioned
stabilizer (solid carrier capable of adsorption) to form an incorporated
formulation or preparation, thereby improving unexpectedly the shelf life
and light resistance of said .alpha.-unsaturated amine derivative or salt.
The acids employed in the present invention include inorganic and organic
acids. Examples of the inorganic acids include perchloric acid,
hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.
Examples of the organic acids include L-ascorbic acid, acetic acid,
succinic acid, benzoic acid, aspartic acid, citric acid, glutamic acid,
oxalic acid, trichloroacetic acid, lactic acid, dichloroacetic acid,
fumaric acid, maleic acid, malic acid, malonic acid, benzenesulfonic acid,
isopropyl acid phosphate, etc. Among them, preferred examples are strong
acids [those wherein the dissociation constant thereof is more than
approximately 1.times.10.sup.-3 or the pK thereof is less than 3 (Iwanami
Rikagaku Jiten, 3rd Edition, 1971, Iwanami Publishing Company, Japan)].
Even in such instances, any of inorganic and organic acids can be used but
preferably inorganic ones are employed. Among them, preferred examples are
listed hereinbelow. Such inorganic acids include perchloric acid,
hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. Such
organic acids include aspartic acid, citric acid, glutamic acid, oxalic
acid, dichloroacetic acid, trichloroacetic acid, fumaric acid, maleic
acid, malonic acid, benzenesulfonic acid, isopropyl acid phosphate, etc.
More preferred examples are phosphoric acid, hydrochloric acid, oxalic
acid, citric acid, benzenesulfonic acid, isopropyl acid phosphate, etc.
Still more preferred examples are phosphoric acid, citric acid,
benzenesulfonic acid, isopropyl acid phosphate, etc. Specifically,
phosphoric acid is most preferable.
The solid carriers employed in the present invention are those capable of
incorporating the .alpha.-unsaturated amine derivatives [I], [II] or salts
thereof. Such solid carriers include those capable of adsorbing at least
5.0.times.10.sup.-2 mmol/g of the active substance from solution or
suspension adjusted to pH.ltoreq.5. Specifically solid carriers capable of
adsorbing from 5.0.times.10.sup.-2 to 400.times.10.sup.-2 mmol/g of the
active substance therefrom are employed. Preferred examples are those
capable of adsorbing from 10.0.times.10.sup.-2 to 200.times.10.sup.-2
mmol/g of the active substance therefrom, more preferably from
10.0.times.10.sup.-2 to 100.times.10.sup.-2 mmol/g of the active substance
therefrom.
Examples of such solid carriers include clay mineral capable of adsorption,
zeolite, activated charcoal, .beta.-cyclodextrin, etc. Examples of such
clay minerals include montmorillonite-saponite groups having 2:1 crystal
structure type form and sepiolite having double-chain crystal structure
type form. Among them, preferred examples are montmorillonite-saponite
groups having 2:1 crystal structure type form.
Examples of such montmorillonite-saponite clay minerals include
montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite,
as well as those containing any of montmorillonite, beidellite,
nontronite, saponite, hectorite, sauconite, and the like as a main
constituent, such as fuller's earth, terra alba, bentonite, and activated
fuller's earth. Fuller's earth is more preferred.
The solid carriers capable of adsorption are not limited to those
exemplified above but may include any substance capable of incorporating
the .alpha.-unsaturated amine derivative [I], [II] or its salt thereinto,
or including (or surrounding) the guest to form a complex such as an
inclusion complex, and a clathrate.
Since conventional clays and kaolin have merely insufficient adsorption
capacity, they do not work for improvement of the stability. Therefore,
they are not suitable for the solid carrier capable of adsorption in the
present invention.
The solid carrier usually employed in the present invention is powdery in
application. The particle size is within 100 .mu.m or less in diameter.
The usual range thereof is from 1 to 100 .mu.m, preferably from 10 to 80
.mu.m. More preferred rages are from 20 to 50 .mu.m.
An amount of the solid carrier (a total amount when two or more solid
carriers are employed) in the composition according to the present
invention is suitably in the range of about 1 to 95 wt% per total of the
final formulation. For example, an appropriate range is about 1 to 90 wt%,
preferably about 1 to 30 wt% in the case of a dust, DL dust, granule, and
microgranule F. It is about 5 to 95 wt%, preferably about 50 to 90 wt% in
the case of a wettable powder, and wettable granule, etc. An amount of
said solid carrier (a total amount when two or more solid carriers are
employed) is in the range of about 10 weight parts or more per one weight
part of the active ingredient, preferably about 10 to 50 weight parts,
more preferably about 10 to 20 weight parts.
An amount of the acid (a total amount when two or more acids are employed)
in the composition according to the present invention is suitably in the
range of about 0.0001 to 10 wt% as a net acid per total of the final
formulation. For example, an appropriate range is about 0.0005 to 5 wt%,
preferably about 0.0005 to 3 wt% in the case of a dust, DL dust, granule,
and microgranule F. It is about 0.5 to 10 wt%, preferably about 0.5 to 5
wt% in the case of a wettable powder, and wettable granule, etc. An amount
of said acid (a total amount when two or more acids are employed) is in
the range of about 0.05 to 0.5 weight parts per one weight part of the
solid carrier, preferably about 0.1 to 0.3 weight parts.
The proportion of the .alpha.-unsaturated amine derivative or salt thereof
in the composition according to the present invention is suitably about
0.1 to 90 wt% per total of the final formulation. For example, an
appropriate range is about 0.1 to 10 wt% in the case of a dust, DL dust,
granule, and microgranule F, about 5 to 90 wt% in the case of a wettable
powder, and wettable granule, etc. An amount of said solid carrier (a
total amount when two or more solid carriers are employed) is in the range
of about 0.1 to 100 weight parts per one weight part of
.alpha.-unsaturated amine derivative or salt thereof, preferably about 0.5
to 50 weight parts.
The agrochemical composition according to the present invention can be
prepared or formulated under pH adjustment according to conventional
methods for preparing agrochemical concentrated dusts. According to one
embodiment, the agrochemical compositions are prepared or formulated by
incorporating the active substance into the solid carrier under a pH 5.5
or less condition. For example, such preparations comprise;
(1) preparing an aqueous solution (or suspension) of at least one of the
active substances, adjusting pH thereof to 5.5 or less, and then mixing
(or blending) the resultant product with the solid carrier, depending on
necessity, in admixture with other agrochemical adjuvants to incorporate
said active substance into said solid carrier;
(2) preparing an aqueous solution (or suspension) of at least one of the
active substances, and a mixture of the acid with the solid carrier,
depending on necessity, in admixture with other agrochemical adjuvants
wherein an amount of the acid employed is sufficient to achieve pH 5.5 or
less in the resultant composition when the aqueous solution (or
suspension) is added, and then mixing said aqueous solution (or
suspension) with said mixture to incorporate said active substance into
said solid carrier;
(3) mixing (or blending) at least one of the active substances, the solid
carrier, and the acid with at least one of other solid carriers wherein an
amount of the acid employed is sufficient to achieve pH 5.5 or less in the
resultant composition when water (or an aqueous solution or suspension) is
added, and then mixing the resultant mixture with said water (or an
aqueous solution or suspension) to incorporate said active substance into
said solid carrier; or
(4) mixing (or blending) at least one of the active substances, and the
solid carrier with at least one of other solid carriers, and then mixing
the resultant mixture with an aqueous solution (or suspension) containing
the acid to incorporate said active substance into or with said solid
carrier wherein an amount of the acid employed is sufficient to achieve pH
5.5 or less in the resultant composition when the aqueous solution (or
suspension) is admixed with said mixture.
The mixing (or blending) or admixing can be carried out by a mixer such as
a mortar and pestle or kneader. The mixing or admixing is not limited to
but may include any of techniques for the preparation of agrochemical
agents or formulations which are well known to those who are skilled in
the art. As the case may be, moisture can be removed by drying after
mixing and incorporation.
Thus, in accordance with the present invention and using the methods used
herein, it is important to adjust the pH of the solution (or suspension)
containing the active substance, etc. to 5.5 or less in advance upon
incorporation of said active substance into or with said stabilizer. The
pH thereof is usually adjusted to 0.01 to 5.5, preferably 0.01 to 4.0,
more preferably 0.1 to 3.0. In a preferred embodiment, a solution (or
suspension) adjusted to pH about 3.0 is employed.
For example, the pH can be controlled by adding several drops of phosphoric
acid into about 500 ml of the aqueous solution (or suspension) in the case
of the above-mentioned processes (1) and (4). However, the pH can be
controlled without any limitation but by means of buffering solutions and
the like. The pH can readily be controlled by adding several drops of
phosphoric acid into the solid carrier in the case of the above-mentioned
processes (2) and (3).
Solvents for the aqueous solution (or suspension) employed in the present
invention include water alone as well as in combination with organic
solvents miscible with water. Preferred systems for the present invention
are those containing water alone in view of agrochemical agents or
formulations.
The stabilized composition according to the present invention is
substantially tolerant to plants as well as human beings and animals
(including fish) at or after an application. Thus, the composition
according to the present invention is safe (harmless) and stable.
The composition according to the present invention is in a solid form. The
composition can be applied as a suitable agrochemical solid formulation or
preparation such as a dust, DL (driftless) dust, granule, wettable powder,
water-dispersible granule, seed treating agent, and microgranule F.
These compositions may be admixed or formulated, if necessary, with other
agrochemically active ingredients, and/or agrochemically acceptable
vehicles such as dispersing agents, spreaders, wetting agents, mucilages,
anti-blocking agents, agglomerating agents, binding agents, antioxidants,
desiccants, etc.
Conventional solid carriers (diluents/extenders) include preferably mineral
powders such as clays (e.g. fine powdered clays, etc.), talcs (e.g. talcum
powder, agalmatolite powder, etc.), silicas (e.g. diatomaceous earth, mica
powder, etc.), vegetable powders (e.g. soybean meal, tobacco powder, wheat
flour, sawdust, etc.), calcium carbonate, sulfur powder, urea powder, and
the like. For this purpose any adjuvant may be employed as long as it is
agrochemically acceptable. These solid carriers may be used individually
or in a suitable mixed form of two or more ingredients in a suitable
ratio.
Surface-active agents (surfactants) which may optionally be employed,
depending on necessity, as said dispersing agent, spreader, wetting agent,
or penetrating agent, include various soaps and nonionic or anionic
surface-active agents such as polyoxyethylene alkyl aryl ethers [e.g.
Noigen.TM. and E.A 142.TM., Dai-ichi Kogyo Seiyaku K.K.], sodium
alkylnaphthalene sulfonates [e.g. Newcalgen BX-C.TM., Takemoto Yushi
K.K.], block copolymers of ethylene oxide and propylene oxide [e.g. Newpol
PE-64.TM., Sanyo Kasei K.K.], polycarboxlate type surface-active agents
[e.g. Toxanon GR-30.TM., Sanyo Kasei K.K.], dialkylsulfosuccinic acid
ester sodium salts [e.g. Neocol SW-C.TM., Dai-ichi Kogyo Seiyaku K.K.],
polyoxyethylene distyrenated phenyl ether sulfate ammonium salts [e.g.
Dixzol 60A.TM., Dai-ichi Kogyo Seiyaku K.K.], sodium lignin sulfonates,
and potassium lignin sulfonates.
The surface-active agents which can be employed as said dispersing agent,
spreader, wetting agent, or penetrating agent include various nonionic and
anionic surface-active agents. Preferred examples of such surface-active
agents include
(1) Nonionic Surface-Active Agents
polyoxyethylene alkyl aryl ethers [e.g. Noigen.TM. and E.A 142.TM.,
Dai-ichi Kogyo Seiyaku K.K.],
block copolymers of ethylene oxide and propylene oxide [e.g. Newpol
PE-64.TM., Sanyo Kasei K.K.],
(2) Anionic Surface-Active Agents
polycarboxlate type surface-active agents [e.g. Toxanon GR-30.TM., Sanyo
Kasei K.K.],
dialkylsulfosuccinic acid ester sodium salts [e.g. Neocol SW-C.TM.,
Dai-ichi Kogyo Seiyaku K.K.],
polyoxyethylene distyrenated phenyl ether sulfate ammonium salts [e.g.
Dixzol 60A.TM., and Dixzol WK.TM., Dai-ichi Kogyo Seiyaku K.K.],
sodium alkylnaphthalene sulfonates [e.g. Newcalgen BX-C.TM., Takemoto Yushi
K.K.],
sodium lignin sulfonates,
potassium lignin sulfonates,
and the like.
A usual amount of the surface-active agents which may be employed in the
composition is suitably in the range of about 0 to 30 wt% per total of the
final formulation. For example, an appropriate range is preferably about 0
to 20 wt%.
Flowing aids include PAP-agents such as isopropyl acid phosphate, talcum,
etc. Such flowing aids are optionally employed in the composition
according to the present invention.
A usual amount of the flowing aids is suitably in the range of about 0 to
20 wt% per total of the final formulation. For example, an appropriate
range is preferably about 0 to 10 wt%.
Anti-blocking agents include white carbon, diatomaceous earth, magnesium
stearate, aluminum oxide, titanium dioxide, etc. Such anti-blocking agents
are optionally employed in the composition according to the present
invention.
A usual amount of the anti-blocking agents is suitably in the range of
about 0 to 50 wt% per total of the final formulation. For example, an
appropriate range is preferably about 0 to 20 wt%.
Agglomerating agents include liquid paraffin, ethylene glycol, diethylene
glycol, triethylene glycol, polyisobutylene (e.g. IP Solvent-2835.TM.,
Idemitsu Sekiyu Kagaku K.K.), etc. Such agglomerating agents are
optionally employed in the composition according to the present invention.
A usual amount of the agglomerating agents is suitably in the range of
about 0 to 20 wt% per total of the final formulation. For example, an
appropriate range is preferably about 0.2 to 10 wt%.
Binding agents include carboxymethylcellulose sodium salt, dextrin,
.alpha.-starch, polyvinyl alcohol, sodium lignin sulfonate, potassium
lignin sulfonate, etc. Such binding agents are optionally employed in the
composition according to the present invention.
A usual amount of the binding agents is suitably in the range of about 0 to
30 wt% per total of the final formulation. For example, an appropriate
range is preferably about 0.2 to 10 wt%.
Antioxidants include dibutylhydroxytoluene,
4,4-thiobis-6-tert-butyl-3-methylphenol, butylhydroxyanisole,
paraoctylphenol, mono-, di- or tri- (a-methylbenzyl)phenol,
2,6-di-tert-butyl-4-methylphenol, pentaerythritol
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)]-propionate, etc. Such
antioxidants are optionally employed in the composition according to the
present invention.
A usual amount of the antioxidants is suitably in the range of about 0 to
30 wt% per total volume of the final formulation. For example, an
appropriate range is preferably about 0 to 10 wt%.
Desiccants include anhydrous gypsum, silica gel powder, etc. Such
desiccants are optionally employed in the composition according to the
present invention.
A usual amount of the desiccants is suitably in the range of about 0 to 30
wt% per total of the final formulation. For example, an appropriate range
is preferably about 0.5 to 20 wt%.
UV adsorbents include 2-(2'-hydroxy-5'-methylphenyl) benzotriazol,
2-ethoxy-2'-ethyloxalic acid bisanilide, succinic acid
dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpireridine
polymeric condensate, etc. Such UV adsorbents are optionally employed in
the composition according to the present invention.
A usual amount of the UV adsorbents is suitably in the range of about 0 to
20 wt% per total of the final formulation. For example, an appropriate
range is preferably about 0.5 to 10 wt%.
UV scattering agents include titanium dioxide, etc. Such UV scattering
agents are optionally employed in the composition according to the present
invention.
A usual amount of the UV scattering agents is suitably in the range of
about 0 to 90 wt% per total of the final formulation. For example, an
appropriate range is preferably about 1.0 to 20 wt%.
The composition containing the .alpha.-unsaturated amine derivative or salt
thereof can be used, as the case may be, in combination with one or more
species of agrochemically active substances such as fungicides (e.g.
organosulfur fungicides, organophosphorus fungicides, organoarsenum
fungicides, organochlorine fungicides, etc.), insecticides (e.g.
organophosphorus insecticides, organochlorine insecticides, carbamate
insecticides, pyrethroid insecticides, etc.), various antibiotics.
Representative examples of said agrochemically active substances include
(the parentheses after the chemical names represent common names or
abbreviations; they are hereinafter often quoted);
Carbamate Insecticides
2-isopropoxyphenyl N-methylcarbamate (PHC, propoxur),
o-cumenyl N-methylcarbamate (MIPC, isoprocarb),
o-sec-butyl N-methylcarbamate (BPMC, fenobucarb),
3,4-xylyl N-methylcarbamate (MPMC, xylylcarb),
m-tolyl N-methylcarbamate (MTMC, metolcarb),
3,5-xylyl N-methylcarbamate (XMC),
2-(ethylthiomethyl)phenyl N-methylcarbamate (ethiofencarb),
1-naphthyl N-methylcarbamate (NAC, carbaryl),
primicarb,
bendiocarb,
carbofuran,
furathiocarb,
carbosulfan,
benfuracarb,
methomyl, etc.;
Pyrethroid Insecticides
cyfluthrin,
permethrin,
cypermethrin,
cyhalothrin,
fenpropathrin,
fenvalerate,
(RS) .alpha.-cyano-3-phenoxybenzyl
(S)-2-(4-difluoromethoxyphenyl)-3-methylbutylate (flucythrinate),
flvalinate,
2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (ethofenprox),
cycloprothrin,
resmethrin,
allethrin,
pyrethrin, etc.;
Organophosphorus Insecticides
MPP (fenthion),
0,0-dimethyl 0-(4-nitro-m-tolyl)thiophosphate (MEP, fenitrothion),
propaphos,
dimethyl p-cyanophenyl thiophosphate (CYAP, cyanophos),
prothiofos,
sulprofos,
profenofos,
EPN,
cyanofenphos,
acephate,
EPS (oxydeprofos),
disulfoton,
thiometon,
PAP (phenthoate),
S-1,2-bis(ethoxycarbonyl)ethyl dimethyl dithiophosphate (malathion),
dimethoate,
vamidothion,
(RS)-[0-1-(4-chloro)pyrazol-4-yl]0-ethyl S-propyl thiophosphate
(pyraclofos),
DEP (trichlorfon),
BRP (naled),
DDVP (dichlorvos),
CVP (chlorfenvinphos),
CVMP (tetrachlorvinphos),
monocrotophos,
phosalone,
chlorpyrifos-methyl,
chlorpyrifos,
pirimiphosmethyl,
diazinon,
etrimfos,
pyridaphenthion,
quinalphos,
isoxathion,
DMTP (methidathion),
dioxabenzofos, etc.;
Organochlorine Insecticides
6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodio
xathiepin 3-oxide (endosulfan), etc.;
Other Insecticides
S,S'-[2-(dimethylamino)trimethylene]bis(thiocarbamate) (cartap),
5-dimethylamino-1,2,3-trithian oxalate (thiocyclam),
S,S'-[2-(dimethylamino)trimethylene]bis(benzenethiosulfonate) (bensultap),
2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiaz
in-4-one (buprofezin),
flufenoxuron,
diflubenzuron,
chlorfluazuron, etc.;
N-Heterocyclic Ergosterol Inhibitor Fungicides
triflumizole,
triforine, etc.;
Carboxamide Fungicides
mepronil,
flutolanil,
pencycuron,
oxycarboxin, etc.;
Dicarboximide Fungicides
iprodione,
vinclozolin,
procymidone, etc.;
Benzimidazole Fungicides
benomyl, etc.;
Polyhaloalkylthio Fungicides
captan, etc.;
Organophosphorus Fungicides
O-ethyl S,S-diphenyl dithiophosphate (EDDP, edifenphos),
O,O-diisopropyl S-benzyl thiophosphate (IBP, iprobenfos), etc.;
Organochlorine Fungicides
4,5,6,7-tetrachlorophthalide (fthalide),
tetrachloroisophthalonitrile (TPN, chlorothalonil),
pentachlorophenol (PCP), etc.;
Organosulfur Fungicides
zinc ethylenebis(dithiocarbamate) (zineb),
manganese ethylenebis(dithiocarbamate) (maneb), etc.;
Organoarsenum Fungicides
iron methanearsonate (MAF),
iron ammonium methanearsonate (MAFA), etc.;
Other Fungicides
diclomezine,
5-methyl-1,2,4-triazolo[3,4-b]benzothiazole (tricyclazole),
pyroquilon,
isoprothiolane,
3-allyloxy-1,2-benzoisothiazole 1,1-dioxide (probenazole),
anilazine,
oxolinic acid,
dimethirimol,
(Z)-2'-methylacetophenone 4,6-dimethylpyrimidine-2-ylhydrazone
(ferimzon), etc.;
Antibiotics
validamycin A,
kasugamycin,
mildiomycin,
blasticidin S,
polyoxin,
oxytetracycline, etc.
Preferred examples of such active ingredients are validamycin A, cartap,
bensultap, probenazole, IBP, tricyclazole, ferimzon, ethofenprox,
flucythrinate, fthalide, MEP, MTMC, BPMC, etc. More preferred examples of
such active ingredients are validamycin A, cartap, bensultap, MEP,
ferimzon, fthalide, etc.
Concrete examples of the mixed compositions according to the present
invention include .alpha.-unsaturated amine derivatives [I], [II] or salt
thereof.validamycin A, .alpha.-unsaturated amine derivatives [I], [II] or
salt thereof.cartap, .alpha.-unsaturated amine derivatives [I], [II] or
salt thereof.bensultap, .alpha.-unsaturated amines [I], [II] or salt
thereof.ferimzon.fthalide, etc.
The proportion of the agrochemically active substances excluding the
.alpha.-unsaturated amine derivative [I], [II] or its salt in the mixed
compositions according to the present invention is of the same value as
mentioned above. Thus, it is suitably about 0.01 to 90 wt % per total of
the final formulation. A total amount of the active substances in the
mixed composition is in the range of about 0.01 to 90 wt %, preferably
about 0.05 to 20 wt %, more preferably about 0.5 to 15 wt % per total of
the final formulation.
Agrochemically active substances which are liquid at ambient temperature or
melt near ambient temperature (e.g. ethofenprox, etc.) may be dissolved or
dispersed in solvents such as high boiling point solvents (e.g.
phenylxylylethane, di-2-ethylhexyladipate, 2-ethylhexylphenylphosphate,
etc.) before use.
According to the present invention, the composition can be employed in
combination with acaricides, miticides, nematocides, herbicides, plant
hormones, plant growth regulators, synergists, attractants, repellents,
pigments, fertilizers, manures, or the like.
In the case where the pesticide of the present invention is in the form of
a wettable powder, it may be employed by diluting, for example, about 30
to 4000 times, preferably 300 to 3000 times, with water before use. A
final concentration of active ingredient is ususally in the range of 5 to
1,000 ppm. A preferred final concentration of the .alpha.-unsaturated
amine derivative or its salt is in the range of 10 to 300 ppm.
The application amount can vary over a wide range, depending on the season,
place and method of application, etc. Preferably, the pesticide of the
invention is employed, in general, in such a manner that the proportion of
the active ingredient (i.e. .alpha.-unsaturated amine and/or salt thereof)
is in the range of 10 to 500 g, more preferably 50 to 300 g, per ten acre.
The compositions according to the present invention are applied to target
pests, for example, by being sprinkled directly over leaves or stems of
plants, by treating soils around roots, or in nursery boxes.
The compositions can be effective in controlling or eradicating
horticultural insect pests and plant parasitic insects, for example, on
rice, vegetables (e.g. cabbage, Japanese cabbage (Brassica rapa L. var.
amplexicaulis T.sub.NAKA et O.sub.NO), Japanese radish (Raphanus sativus
L. var. hortensis B.sub.ACKER), cucumber, potato, etc.), fruit trees (e.g.
citrus, pear, etc.), tea, tobacco, and the like. Such pests include
Lepidoptera pests such as, for example, Chilo suppressalis, Cnaphalocrocis
medinalis, Pseudaletia separata, Mamestra brassicae, Plutella xylostella,
Caloptilia theivora, Adoxophyes sp.; Coleoptera pests such as, for
example, Lissorhoptrus oryzophilus, Echinocnemus squameus, Oulema oryzae,
Aulacophora femoralis; Hemiptera pests such as, for example, Nephotettix
cincticeps, Nilaparvata lugens, Laodelphax striatellus, Sogatella
furcifera, Trialeurodes vaporariorum, Bemisia tabaci, Psylla pyricola;
Aphids such as, for example, Aphis gossypii, Myzus persicae, Macrosiphum
euphorbiae; Thysanoptera pests such as, for example, Scirtothrips
dorsalis, Thrips palmi; etc.
Examples of these pests include Asiatic rice borer (rice stem borer,
striped rice borer), rice leafroller (rice leaffolder), armyworm (rice
armyworm, rice ear-cutting caterpillar), cabbage armyworm, diamondback
(cabbage moth), tea leafroller, tea tortorix, rice water weevil, rice
curculio (rice plant weevil), rice leaf beetle, cucurbit leaf beetle,
green rice leafhopper, whitebacked rice planthopper, brown rice
planthopper, small brown planthopper, greenhouse whitefly (glasshouse
whitefly), sweetpotato whitefly, pear psylla, cotton aphid (melon aphid),
green peach aphid, peach-potato aphid, potato aphid (tomato aphid), yellow
tea thrips, chillie thrips, etc.
The compositions can be applied to insect habitats (for example, breeding
or swarming areas) in a permanently preventive (i.e. before infestation)
or eradicative manner (i.e. after infestation).
The compositions of the present invention can be prepared according to the
methods described herein or in the working examples.
Preferred compositions according to the present invention are DL dusts,
granules, and wettable powders.
A preferred composition of DL dusts contains:
active substance (.alpha.-unsaturated amine [I] and/or salt thereof, etc.)
solid carrier (fuller's earth, etc.)
acid (phosphoric acid, etc.)
fixing agent (anionic surface-active agent [Neocol SW-C.TM., etc.], etc.)
and
DL agent (IP Solvent.TM., etc.).
A preferred composition of granules contains:
active substance (.alpha.-unsaturated amine [I] and/or salt thereof, etc.)
solid carrier (fuller's earth, etc.)
acid (phosphoric acid, etc.)
binding agent (dextrin, etc.)
penetrating agent (anionic surface-active agent [Toxanon GR-30.TM., etc.],
etc.) and
bulking agent (clay, etc.).
A preferred composition of wettable powders contains:
active substance (.alpha.-unsaturated amine [I] and/or salt thereof, etc.)
solid carrier (fuller's earth, etc.)
acid (phosphoric acid, etc.) and
dispersing agent (anionic surface-active agent [Dixzol WK.TM., etc.],
etc.).
A more preferred composition of DL dusts contains:
active substance (.alpha.-unsaturated amine [II] and/or salt thereof, etc.)
solid carrier (fuller's earth, etc.)
acid (phosphoric acid, etc.)
fixing agent (anionic surface-active agent [Neocol SW-C.TM., etc.], etc.)
and
DL agent (IP Solvent.TM., etc.).
A more preferred composition of granules contains:
active substance (.alpha.-unsaturated amine [II] and/or salt thereof, etc.)
solid carrier (fuller's earth, etc.)
acid (phosphoric acid, etc.)
binding agent (dextrin, etc.)
penetrating agent (anionic surface-active agent [Toxanon GR-30.TM., etc.],
etc.) and
bulking agent (clay, etc.).
A more preferred composition of wettable powders contains:
active substance (.alpha.-unsaturated amine [II] and/or salt thereof, etc.)
solid carrier (fuller's earth, etc.)
acid (phosphoric acid, etc.) and
dispersing agent (anionic surface-active agent [Dixzol WK.TM., etc.],
etc.).
The compositions according to the present invention can inhibit the
degradation of the .alpha.-unsaturated amine derivative [I], [II] or its
salt even when they are stored for long time and prevent the
photodegradation by sunlight even when they are sprinkled on paddy and
upland fields, thereby being stable, exerting essentially no adverse
effect on plants and advantageously useful in controlling, combatting or
preventing plant pests or harmful organisms.
Further, the compositions according to the present invention can include
other agrochemical active substances which could not be admixed with the
.alpha.-unsaturated amine derivatives [I], [II] or salts thereof in the
prior art formulations.
Still, the compositions according to the present invention have an
excellent availability of the active ingredient after application.
Advantageously, the compositions according to the present invention can be
readily manufactured by industrial processes.
The pesticidal composition thus obtained is extremely low in toxicity and
is stable, safe and excellent as an agrochemical. It can be used in the
same manner as in conventional insecticides and exert superior stability
in comparison with conventional products.
The foregoing is merely illustrative of the invention and is not intended
to limit the invention to the disclosed compounds and compositions.
EXAMPLES
By the following reference examples, working examples, and test examples,
the present invention will be explained more concretely, but they should
not be interpreted as limiting the invention in any manner.
REFERENCE EXAMPLE 1
DL Type Dust (no solid carrier capable of adsorption, and without pH
adjustment)
To 98.25 parts of fine powdered clay was added 0.25 parts of Compound No.
3, followed by 1.0 parts of liquid parafin (Driless C.TM., hereinafter
"Driless C.TM.") and 0.5 parts of white carbon, and the resulting mixture
was well mixed by an automated mortar. The mixture was then triturated by
Bantam mill to afford DL type dusts containing Compound No. 3.
REFERENCE EXAMPLE 2
DL Type Dust (no solid carrier capable of adsorption, and without pH
adjustment; admixture with cartap)
To 96.25 parts of fine powdered clay was added 0.25 parts of Compound No.
3, followed by 2.0 parts of cartap, 1.0 parts of Driless C.TM. and 0.5
parts of white carbon, and the resulting mixture was well mixed by an
automated mortar. The mixture was then triturated by Bantam mill to afford
DL type dusts containing the mixture of Compound No. 3 and cartap.
REFERENCE EXAMPLE 3
DL Type Dust (no solid carrier capable of adsorption, and without pH
adjustment; admixture with validamycin A)
To 97.95 parts of fine powdered clay was added 0.25 parts of Compound No.
3, followed by 0.3 parts of validamycin A, 1.0 parts of Driless C.TM. and
0.5 parts of white carbon, and the resulting mixture was well mixed by an
automated mortar. The mixture was then triturated by Bantam mill to afford
DL type dusts containing the mixture of Compound No. 3 and validamycin A.
REFERENCE EXAMPLE 4
DL Type Dust (no solid carrier capable of adsorption, and without pH
adjustment; admixture with ferimzon and fthalide)
To 94.75 parts of fine powdered clay was added 0.25 parts of Compound No.
3, followed by 2.0 parts of ferimzon, 1.5 parts of fthalide, 1.0 parts of
Driless C.TM. and 0.5 parts of white carbon, and the resulting mixture was
well mixed by an automated mortar. The mixture was then triturated by
Bantam mill to afford DL type dusts containing the mixture of Compound No.
3, ferimzon, and fthalide.
REFERENCE EXAMPLE 5
Granule (no solid carrier capable of adsorption)
To 93.0 parts of fine powdered clay was added 1.0 parts of Compound No. 3,
followed by 5.0 parts of dextrin and 1.0 parts of 85% phosphoric acid, and
the resulting mixture was well mixed. To the mixture was added water and
the wet mixture was well kneaded. The damp mass was granulated through an
oscillating granulator (screen size: 1.0 mm in diameter) to form wet
products. The products was dried and sieved to granules ranging from
10-mesh to 32-mesh.
REFERENCE EXAMPLE 6
Wettable Powder (no solid carrier capable of adsorption, and without pH
adjustment)
To 82.0 parts of clay for a wettable powder was added 10.0 parts of
Compound No. 3, followed by 5.0 parts of Newcalgen BX-C.TM. (Takemoto
Yushi K.K., Japan) and 3.0 parts of white carbon, and the resulting
mixture was well blended by an automated mortar. The mixture was
pulverized by a fine grinding mill to afford wettable powders containing
the mixture of Compound No. 3.
REFERENCE EXAMPLE 7
DL Type Dust (no solid carrier capable of adsorption, and without pH
adjustment)
Compound No. 3 (20.0 parts) was dissolved in 80.0 parts of water (adjusted
to pH 3). The solution (1.25 parts) was blended well with 5.0 parts of
fine powdered clay. To 6.25 parts of the resulting mixture was added 7.25
parts of fine powdered clay, followed by 1.0 parts of Driless C.TM., 0.5
parts of white carbon and 15.0 parts of anhydrous gypsum and the mixture
was well blended by an automated mortar. The mixture was then triturated
by Bantam mill to afford DL type dusts containing Compound No. 3.
REFERENCE EXAMPLE 8
DL Type Dust
To 93.25 parts of fine powdered clay was added 0.25 parts of Compound No.
3, followed by 1.0 parts of Driless.TM., 5.0 parts of fuller's earth and
0.5 parts of white carbon, and the resulting mixture was well mixed by an
automated mortar. The mixture was then triturated by Bantam mill to afford
DL type dusts containing Compound No. 3.
EXAMPLE 1
DL Type Dust (Process 1)
Compound No. 3 (20.0 parts) was dissolved in 80.0 parts of water
(previously adjusted with phosphoric acid to pH 3 by measuring with a pH
meter). The solution (1.25 parts) was blended well with 5.0 parts of
fuller's earth to become homogeneous. To 6.25 parts of the resulting
mixture was added 77.25 parts of fine powdered clay, followed by 1.0 parts
of Driless C.TM., 0.5 parts of white carbon and 15.0 parts of anhydrous
gypsum and the mixture was well blended by an automated mortar. The
mixture was then triturated by Bantam mill to afford DL type dusts
containing Compound No. 3.
EXAMPLE 2
DL Type Dust (Process 1)
Compound No. 3 (20.0 parts) was dissolved in 80.0 parts of water
(previously adjusted with phosphoric acid to pH 3 by measuring with a pH
meter). The solution (1.25 parts) was blended well with 5.0 parts of
fuller's earth, 77.25 parts of fine powdered clay, 1.0 parts of Driless
C.TM., 0.5 parts of white carbon and 15.0 parts of anhydrous gypsum, and
the resulting mixture was well blended by an automated mortar. The mixture
was then triturated by Bantam mill to afford DL type dusts containing
Compound No. 3.
EXAMPLE 3
DL Type Dust (Process 1)
Compound No. 3 (20.0 parts) was dissolved in 80.0 parts of water
(previously adjusted with phosphoric acid to pH 3 by measuring with a pH
meter). The solution (1.25 parts) was blended well with 5.0 parts of
sepiolite (Aidplus.TM., Takeda Chemical Industries, Ltd) to become
homogeneous. To 6.25 parts of the resulting mixture was added 77.25 parts
of fine powdered clay, followed by 1.0 parts of Driless C.TM., 0.5 parts
of white carbon and 15.0 parts of anhydrous gypsum, and the resulting
mixture was well blended by an automated mortar. The mixture was then
triturated by Bantam mill to afford DL type dusts containing Compound No.
3.
EXAMPLE 4
DL Type Dust (Process 1)
Compound No. 3 (20.0 parts) was dissolved in 80.0 parts of water
(previously adjusted with phosphoric acid to pH 3 by measuring with a pH
meter). The solution (1.25 parts) was blended well with 5.0 parts of
.beta.-cyclodextrin to become homogeneous. To 6.25 parts of the resulting
mixture was added 77.25 parts of fine powdered clay, followed by 1.0 parts
of Driless C.TM., 0.5 parts of white carbon and 15.0 parts of anhydrous
gypsum, and the resulting mixture was well blended by an automated mortar.
The mixture was then triturated by Bantam mill to afford DL type dusts
containing Compound No. 3.
EXAMPLE 5
DL Type Dust (Process 1)
Compound No. 3 (20.0 parts) was dissolved in 80.0 parts of water
(previously adjusted with phosphoric acid to pH 3 by measuring with a pH
meter). The solution (1.25 parts) was blended well with 5.0 parts of
fuller's earth by an automated mortar to become homogeneous. To 6.25 parts
of the resulting mixture was added 76.95 parts of fine powdered clay,
followed by 0.3 parts of validamycin A, 1.0 parts of Driless C.TM., 0.5
parts of white carbon and 15.0 parts of anhydrous gypsum, and the
resulting mixture was well blended by an automated mortar. The mixture was
then triturated by Bantam mill to afford DL type dusts containing the
mixture of Compound No. 3 and validamycin A.
EXAMPLE 6
DL Type Dust (Process 1)
Compound No. 3 (20.0 parts) was dissolved in 80.0 parts of water
(previously adjusted with phosphoric acid to pH 3 by measuring with a pH
meter). The solution (1.25 parts) was blended well with 5.0 parts of
fuller's earth by an automated mortar to become homogeneous. To 6.25 parts
of the resulting mixture was added 75.25 parts of fine powdered clay,
followed by 2.0 parts of cartap, 1.0 parts of Driless C.TM., 0.5 parts of
white carbon and 15.0 parts of anhydrous gypsum, and the resulting mixture
was well blended by an automated mortar. The mixture was then triturated
by Bantam mill to afford DL type dusts containing the mixture of Compound
No. 3 and cartap.
EXAMPLE 7
DL Type Dust (Process 1)
Compound No. 3 (15.0 parts) was mixed and dissolved with 55.0 parts of
water and 30.0 parts of phosphoric acid. The solution (1.75 parts) was
blended well with 5.0 parts of fuller's earth by an automated mortar to
become homogeneous. To 6.75 parts of the resulting mixture was added 76.75
parts of fine powdered clay, followed by 1.0 parts of IP Solvent.TM., 0.5
parts of white carbon and 15.0 parts of anhydrous gypsum, and the
resulting mixture was well blended by an automated mortar. The mixture was
then triturated by Bantam mill to afford DL type dusts containing Compound
No. 3. The 10% suspension of the DL type dust was measured by a pH meter
to exhibit pH 4.5.
EXAMPLE 8
DL Type Dust (Process 2)
Compound No.3 (20.0 parts) was dissolved in 80.0 parts of water. The
aqueous solution (1.25 parts) was added to a mixture of phosphoric acid
(0.5 parts) and fuller's earth (5.0 parts) (previously blended well). The
resulting mixture was well blended by an automated mortar to become
homogeneous. Then the mixture was dried at 60.degree. C. in vacuo. To 5.75
parts of the dried mixture was added 77.75 parts of fine powdered clay,
followed by 1.0 parts of IP Solvent.TM., 0.5 parts of white carbon and
15.0 parts of anhydrous gypsum, and the resulting mixture was well blended
by an automated mortar. The mixture was then triturated by Bantam mill to
afford DL type dusts containing Compound No.3. The 10% suspension of the
DL type dust was measured by a pH meter to exhibit pH 4.5.
EXAMPLE 9
DL Type Dust (Process 1)
Compound No.3 (2.0 parts) was dissolved in 58.0 parts of water (previously
adjusted with phosphoric acid to pH 3 by measuring with a pH meter). The
solution (60.0 parts) was blended well with 40.0 parts of fuller's earth
to become homogeneous and the resulting mixture was dried by a spray-dryer
(L-8 Type, Ohokawara Kakouki K. K., Japan). To 5.5 parts of the dried
mixture was added 91.5 parts of fine powdered clay, followed by 0.5 parts
of IP Solvent.TM., 0.5 parts of ultra-pure, microparticle aluminum oxide
and 2.0 parts of Neocol SW-C.TM., and the resulting mixture was well
blended by an automated mortar. The mixture was then triturated by Bantam
mill to afford DL type dusts containing Compound No.3.
EXAMPLE 10
DL Type Dust (Process 1)
Compound No.1 (20.0 parts) was dissolved in 80.0 parts of water (previously
adjusted with phosphoric acid to pH 3 by measuring with a pH meter). The
solution (1.25 parts) was blended well with 5.0 parts of fuller's earth by
an automated mortar to become homogeneous. To 6.25 parts of the resulting
mixture was added 77.25 parts of fine powdered clay, followed by 1.0 parts
of IP Solvent.TM., 0.5 parts of white carbon and 15.0 parts of anhydrous
gypsum, and the resulting mixture was well blended by an automated mortar.
The mixture was then triturated by Bantam mill to afford DL type dusts
containing Compound No.1.
EXAMPLE 11
DL Type Dust (Process 1)
Compound No.1 (20.0 parts) was dissolved in 80.0 parts of water (previously
adjusted with phosphoric acid to pH 3 by measuring with a pH meter). To
1.25 parts of the solution was added 5.0 parts of fuller's earth, followed
by 77.25 parts of fine powdered clay, 1.0 parts of Driless C.TM., 0.5
parts of white carbon and 15.0 parts of anhydrous gypsum, and the
resulting mixture was well blended by an automated mortar. The mixture was
then triturated by Bantam mill to afford DL type dusts containing Compound
No.1.
EXAMPLE 12
DL Type Dust (Process 1)
Compound No.1 (15.0 parts) was mixed and dissolved with 55.0 parts of water
and 30.0 parts of phosphoric acid. The solution (1.75 parts) was blended
well with 5.0 parts of fuller's earth by an automated mortar to become
homogeneous. To 6.25 parts of the resulting mixture was added 77.25 parts
of fine powdered clay, followed by 1.0 parts of IP Solvent.TM., 0.5 parts
of white carbon and 15.0 parts of anhydrous gypsum, and the resulting
mixture was well blended by an automated mortar. The mixture was then
triturated by Bantam mill to afford DL type dusts containing Compound
No.1. The 10% suspension of the DL type dust was measured by a pH meter to
exhibit pH 4.3.
EXAMPLE 13
DL Type Dust (Process 2)
Compound No.1 (20.0 parts) was dissolved in 80.0 parts of water. The
aqueous solution (1.25 parts) was added to a mixture of phosphoric acid
(0.5 parts) and fuller's earth (5.0 parts) (previously blended well). The
resulting mixture was well blended by an automated mortar to become
homogeneous. Then the mixture was dried at 60.degree. C. in vacuo. To 5.75
parts of the dried mixture was added 77.75 parts of fine powdered clay,
followed by 1.0 parts of IP Solvent.TM., 0.5 parts of white carbon and
15.0 parts of anhydrous gypsum, and the resulting mixture was well blended
by an automated mortar. The mixture was then triturated by Bantam mill to
afford DL type dusts containing Compound No.1. The 10% suspension of the
DL type dust was measured by a pH meter to exhibit pH 4.4.
EXAMPLE 14
Granule (Process 3)
To 83.0 parts of fine powdered clay was added 10.0 parts of fuller's earth,
followed by 1.0 parts of Compound No.3, 5.0 parts of dextrin and 1.0 parts
of 85% phosphoric acid, and the resulting mixture was well mixed. To the
mixture was added water and the wet mixture was well kneaded. The damp
mass was granulated through an oscillating granulator (screen size: 1.0 mm
in diameter) to form wet products. The products was dried and sieved to
granules ranging from 10-mesh to 32-mesh. After pulverization of the
granules, the 10% suspension thereof was measured by a pH meter to exhibit
pH 3.1.
EXAMPLE 15
Granule (Process 4)
To 83.0 parts of fine powdered clay was added 10.0 parts of fuller's earth,
followed by 1.0 parts of Compound No.3, 5.0 parts of dextrin, and the
resulting mixture was well mixed. To the mixture was added an aqueous
solution containing 1.0 parts of 85% phosphoric acid and the wet mixture
was well kneaded. The damp mass was granulated through an oscillating
granulator (screen size: 1.0 mm in diameter) to form wet products. The
products was dried and sieved to granules ranging from 10-mesh to 32-mesh.
After pulverization of the granules, the 10% suspension thereof was
measured by a pH meter to exhibit pH 3.0.
EXAMPLE 16
Wettable Powder (Process 4)
To 77.0 parts of fuller's earth was added 10.0 parts of Compound No.3,
followed by 5.0 parts of 85% phosphoric acid, 5.0 parts of Newcalgen
BX-C.TM. (Takemoto Yushi K. K., Japan) and 3.0 parts of white carbon, and
the resulting mixture was well blended by an automated mortar. The mixture
was pulverized by a fine grinding mill to afford wettable powders.
EXPERIMENTAL EXAMPLE 1
Shelf Life Stability Test
Each mixed formulation obtained in Examples 1 to 16 and Reference Examples
1 to 8 (each 20 g) was stored at a determined temperature for a determined
time in a paper pack for powdery dusts, paper pack for granules, or
aluminum pack for wettable powders. Then the sample was taken out of the
pack. A determined amount of the sample (10 mg as .alpha.-unsaturated
amine derivatives or salts thereof) was measured accurately, and extracted
by shaking with 40 ml of acetonitrile: 0.5M aq. KH.sub.2 PO.sub.4 -50/50
(v/v) for 30 min.
A content of .alpha.-unsaturated amine derivatives or salts thereof in the
extract was measured by high performance liquid chromatography (HPLC,
column; Nucleosil 10-C.sub.18, Gaschro, Industries, K. K., Japan; eluting
solvent; acetonitrile: 0.5M aq. KH.sub.2 PO.sub.4 -50/50 (v/v)).
A degradation percent (%) of .alpha.-unsaturated amine derivatives or salts
thereof was calculated according to the following formula:
##EQU1##
The results are shown in Tables 1 to 3.
TABLE 1
______________________________________
Shelf Life of .alpha.-Unsaturated Amine Derivatives or
Salts Thereof in Single or Mixed DL Type Dusts
Degradation of
.alpha.-Unsaturated
Amine Derivatives
or Salts Thereof
Test Preparation
Stabilizer at 40.degree. C. for 2 months
______________________________________
Example 1 Fuller's earth
1.5%
Example 2 Fuller's earth
1.7%
Example 3 Sepiolite 7.3%
Example 4 .beta.-Cyclodextrin
3.3%
Example 5 Fuller's earth
1.6%
Example 6 Fuller's earth
1.7%
Example 7 Fuller's earth
1.2%
Example 8 Fuller's earth
3.2%
Control:
Reference None 21.6%
Example 1
Reference Fine powdered clay
36.3%
Example 7
Reference Fuller's earth
17.8%
Example 8 (None of acid)
______________________________________
TABLE 2
______________________________________
Shelf Life of .alpha.-Unsaturated Amine Derivatives
or Salts Thereof in Granules
Degradation of .alpha.-Unsaturated
Amine Derivatives or Salts
Test Preparation
Stabilizer Thereof at 40.degree. C. for 2 months
______________________________________
Example 14 Fuller's earth
4.1%
Control:
Reference None 17.7%
Example 5
______________________________________
TABLE 3
______________________________________
Shelf Life of .alpha.-Unsaturated Amine Derivatives
or Salts Thereof in Wettable Powders
Degradation of .alpha.-Unsaturated
Amine Derivatives or Salts
Test Preparation
Stabilizer Thereof at 40.degree. C. for 2 months
______________________________________
Example 16 Fuller's earth
1.2%
Control:
Reference None 10.3%
Example 6
______________________________________
EXPERIMENTAL EXAMPLE 2
Stability Test for Photolytic Degradation
The formulation obtained in Example 8 and Reference Example 6 (each 1 g)
was diluted with 1,000 ml of water to form a 1,000-fold dilution. The
dilution (5 ml) was put into a Petri dish (diameter: 8.6 cm.times.height:
2.0 cm) homogeneously, and then dried at 60.degree. C. for 2 hours in
vacuo. The duplicate samples were prepared, i.e. one for dark and the
other for exposure to sunlight.
After the exposure to sunlight, the .alpha.-unsaturated amine derivative or
its salt was extracted by shaking with 50 ml of acetonitrile: 0.5M aq.
KH.sub.2 PO.sub.4 -50/50 (v/v).
A content of .alpha.-unsaturated amine derivatives or salts thereof in the
extract was measured by high performance liquid chromatography (HPLC,
column; Nucleosil 10-C.sub.18, Gaschro, Industries, K. K.; eluting
solvent; acetonitrile: 0.5M aq. KH.sub.2 PO.sub.4 -50/50 (v/v)).
TABLE 4
______________________________________
Resistance against Photodegradation of
.alpha.-Unsaturated Amine Derivatives or Salts
Thereof after Sprinkling Wettable Powders
Recovery of .alpha.-Unsaturated
Amine Derivatives or Salts
Residual
Test Preparation
Thereof at 40.degree. C. for 2 months
Ratio
______________________________________
Example 16
(Dark) 96.1% 100.0%
Example 16
(Sun- 79.6% 88.3%
light)
Control:
Reference
(Dark) 97.5% 100.0%
Example 6
Reference
(Sun- 33.5% 34.3%
Example 6
light)
______________________________________
Recovery: Recover ratio of unsaturated amine derivatives or salts thereof
to added amounts
Residual Ratio: Determined value of residual unsaturated amine derivative
or salts thereof in preparations exosed to the sunlight versus those in
the dark (= 100).
EXPERIMENTAL EXAMPLE 3
Adsorption Test
Five hundred milligrams of Compound 3 was measured accurately, put into a
100 ml glass cylindrical graduate, and dissolved in purified water
(adjusted previously to pH 3 or 6) to form a determined volume.
Five hundred milligrams of fuller's earth was measured accurately, and put
into a 100 ml Erlenmeyer flask. To the Erlenmeyer flask was added said
solution by means of a 40 ml volumetric pipette. The resulting suspension
was shaken at 26.degree. C. for 3 hours.
After removal of the fuller's earth by centrifugation at 3000 rpm, the
concentration of Compound 3 in the supernatant was measured by high
performance liquid chromatography (HPLC, column; Nucleosil 10-C.sub.18,
Gaschro, Industries, K. K.; eluting solvent; acetonitrile: 0.5M aq.
KH.sub.2 PO.sub.4 -50/50 (v/v)). An amount of Compound 3 incorporated into
the fuller's earth was estimated from the observation.
TABLE 5
______________________________________
Adsorption of .alpha.-Unsaturated Amine Derivatives
or Salts Thereof on Fuller's Earth
Adsorption Amount of .alpha.-Unsaturated Amine
Derivatives Salts Thereof on Fuller's earth
pH (mmol/g)
______________________________________
3 42.6 .times. 10.sup.-2
6 10.9 .times. 10.sup.-2
______________________________________
The adsorption amount was calculated according to the following formula:
Adsorption=(Compound 3 in the Aqueous Solution-Compound 3 in the
Supernatant)/fuller's earth Added
EXPERIMENTAL EXAMPLE 4
Adsorption Test
An amount of the adsorbed compound on the fine powdered clay at pH 3,0 was
measured in the same manner as in Experimental Example 3.
TABLE 6
______________________________________
Adsorption of .alpha.-Unsaturated Amine Derivatives
or Salts Thereof on Fine Powdered Clay
Adsorption Amount of .alpha.-Unsaturated Amine
Derivatives Salts Thereof on Fine Powdered Clay
pH (mmol/g)
______________________________________
3 3.1 .times. 10.sup.-2
______________________________________
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